CN105722768B

CN105722768B - Water-soluble sustained release capsule, correlation technique and correlated product

Info

Publication number: CN105722768B
Application number: CN201480062291.5A
Authority: CN
Inventors: S·库马尔; 大卫·M·李
Original assignee: Monosol LLC
Current assignee: Monosol LLC
Priority date: 2013-10-07
Filing date: 2014-10-06
Publication date: 2019-02-19
Anticipated expiration: 2034-10-06
Also published as: JP6691478B2; JP2017500376A; US20150126426A1; WO2015054100A3; KR20160065205A; CN105722768A; EP3055403B1; EP3055403A2; WO2015054100A2; US9670437B2

Abstract

Disclosed herein is the capsules for the ingredient being contained therein for sustained release, in particular for sustained release water sensitivity gas-generating agent composition, other water-soluble capsules at gas composition or other cleaning combinations into water-based liquid medium.The sustained release capsule includes one or more deflation pin holes, the deflation pin hole is to contain production gas water sensitivity in capsule or other at gas composition, such as it is intended for inorganic bleaching agents or other alkaline compositions or essence of the sustained release into washing medium during laundry cycles.Such as by exposure to ambient water vapor, the pin hole allows gas to generate in capsule or formed in other ways, to escape from capsule, prevents pressure build-up and capsule deformation during storage.The pin hole is sized to prevent from when being immersed in liquid medium (for example, liquid water in water-based liquid medium) or substantially limit liquid in other ways to pass through.Also disclose the correlated product and method for delivering the capsule combined with detergent or other laundry compositions.

Description

Water-soluble sustained release capsule, correlation technique and correlated product

Cross reference to related applications

According to 35U.S.C. § 119 (e), there is a requirement that the U.S. Provisional Patent Application the 61/th that on October 7th, 2014 submits 887, No. 532 equity, and the disclosure of which is incorporated herein by reference herein.

Technical field

Present disclosure relate generally to cleaning combination and the ingredient that is contained therein for sustained release it is water-soluble Property capsule.More specifically, this disclosure relates to contain the production gas water sensitivity composition in capsule, such as wishing Inorganic bleaching agents or other alkaline compositions of the sustained release into washing medium includes one or more during laundry cycles The water-soluble capsule of a deflation pin hole.

Background technique

Water-soluble polymer films are commonly used for packaging material with the material for simply distributing, toppling over, dissolve and dispensing is to be delivered.Example Such as, the parcel made of water-solubility membrane is usually used in packing home care compositions, for example, small containing clothing or dish washing agent Bag.Pouch can be added directly to the mixing vessel of such as bucket, slot or rinsing maching by consumer.This advantageously provides accurate dispensing, The needs that consumer measures composition are eliminated simultaneously.The pouch can also reduce will with distribute analogous composition from container, such as The relevant confusion of pouring liquid laundry detergent compositions from bottle.The pouch is also isolated in composition therein and the hand of user connects Touching.In short, the soluble polymeric film parcel comprising premeasuring reagent provides consumer's convenience used in numerous applications.

It, can if introducing alkaline components (for example, bleaching additive) in the second stage for for example postponing 15 to 20 minutes The effect of to increase certain laundry actives (for example, enzyme).

There is still a need for have required sustained release characteristic, enough solubility to wash in cold, warm or hot laundry water Any residue, chemically and physically compatibility and ideal with laundry ingredient will not be left when end cycle on wash load Engineering properties (including good machinability) water-soluble delivery medium.

Summary of the invention

The disclosure relates generally to the capsule for the ingredient being contained therein for sustained release, is especially used for sustained release Composition (including but not limited to water sensitivity gas-generating agent composition, other gas-generating agent compositions, air exhaust combination object, essence, other fragrance Agent, other volatile compositions and cleaning combination) water-soluble capsule into water-based liquid medium.

For a variety of materials of the sustained release into aqueous medium itself be it is water-sensitive, have when and liquid or vaporous water The trend of gas is produced when contact.For example, being suitble in laundry applications the mixing as the SODIUM PERCARBONATE of inorganic bleaching agents and sodium carbonate Object produces in the presence of liquid or vaporous water, such as in moist (for example, 80% relative humidity) and high temperature (for example, 38 DEG C) environment Gas.SODIUM PERCARBONATE and sodium carbonate and water directly generate hydrogen peroxide gas when contacting, and hydrogen peroxide gas is further decomposed Cheng Shui and oxygen.Such gas, which generates, can assemble and cause in the sealing container (for example, capsule) for accommodating water sensitivity composition Undesirable pressure rise.Since capsule is designed in hydrotropism's liquid medium (for example, aqueous in laundry cycles is washed Wash fluid) its water sensitivity composition is discharged when delay time through controlling after addition capsule, therefore capsule is necessary for water at this Barrier in delay time.However, capsule also becomes airtight by keeping capsule waterproof, this is in the case where positive degassing Lead to the dangerous pressure build-up in capsule, because can produce in capsule from external environment by the vapor that capsule wall is spread The gas of capture.

Such as using the capsule system based on water-soluble polymer (for example, being formed by polyvinyl alcohol polymer The SODIUM PERCARBONATE and sodium carbonate delivered in capsule) sustained release inorganic bleaching agents laundry specificity embodiment in, capsule reason It is slowly dissolved with thinking, and at nominal 40 DEG C, keeps after the addition of fully functional and hydrotropism's liquid medium about 15~20 minutes The interior water to large volume is impenetrable.The delay time is preferably, because if postponing in 40 DEG C of washing cycle About 15~20 minutes second stage introduce more basic activated dose (for example, inorganic bleaching agents), then can increase certain laundries The effect of ingredient (for example, enzyme).Other than the delayed dissolved within the desired minimum time and ingredient discharge, capsule is ideally Sufficiently soluble to prevent residue from staying on wash load at the end of washing cycle, especially for about 30 minutes or 45 points 60 minutes or 75 minutes washing cycles of Zhong Zhiyue are (for example, can wherein be defined as washing cycle arranging from introducing water to first time The time that water/swing circle starts).Capsule also suitably with any other laundry detergent compositions to be added into washing medium Or composition chemistry and physical compatibility, no matter separating or combining with capsule (for example, in the water-solubility membrane pouch comprising two kinds of components In).

In view of these problems and desired character for sustained release water sensitivity ingredient, this disclosure relates to contain Production gas water sensitivity composition in capsule, especially for wishing that sustained release is into washing medium during laundry cycles The capsule comprising one or more deflation pin holes of inorganic bleaching agents or other alkaline compositions.It is steamed by exposure to ambient water Gas, pin hole allow gas to generate in capsule, to escape from capsule, prevent pressure build-up and capsule during storage from becoming Shape.Pin hole is sized to prevent when being immersed in liquid medium (for example, liquid water in water-based liquid medium) Or it substantially limits liquid in other ways and passes through.

Allow comprising appropriately sized pin hole using the capsule delivery medium applied for sustained release, regardless of whether needle To water sensitivity composition, other gas-generating agent compositions, air exhaust combination object, essence or other flavouring agents, volatile compositions, cleaning group Close object or other compositions.In laundry applications, this allows using the relatively thick capsule wall with selected thickness (for example, phase For relatively thin water-solubility membrane pouch) cold water soluble polymers (for example, cold water soluble polyvinyl alcohol grade resins), to mention For the desired time for sustained release.With hot water solubility's polymer film formula (for example, hot water solubility's polyvinyl alcohol) It compares, cold water soluble polymers carry out in an excellent manner in the case where no residue is retained on clothing.In addition to not Must using except hot water solubility's film, the protective coating (for example, polyethylene glycol) on bleaching agent be also it is unwanted because thick The excellent barrier of capsule wall provides the environmental protection appropriate to its content.Equally, because bleaching agent does not need to protect Coating is protected, is also not necessarily solid monolithic form (e.g., including the compressed tablets of bleaching agent and adhesive), thus allows to make With the bleaching agent of powder type

An aspect of this disclosure is related to the sustained release capsule for delivering compositions, and the capsule includes: that (a) includes Water-soluble polymer and limit sealing inside capsule volume capsule shells, wherein the capsule shells have about 100 μm to about Wall thickness in the range of 5000 μm；(b) composition for sustained release being contained in the inside capsule volume of sealing.

The another aspect of present disclosure is related to the capsule for delivering compositions, and the capsule includes: that (a) includes water-soluble Property polymer and limit the capsule shells of internal capsule volume, wherein (i) capsule shells have about 100 μm to about 5000 μm of model Interior wall thickness is enclosed, and (ii) described capsule shells include pin hole, the pin hole is sized with shape to which (A) is allowed in inside Gaseous fluid communicates between environment outside capsule volume and capsule shells, and (B) is limited in internal capsule volume and external rings Liquid fluid communicates between border；(b) composition being contained in internal capsule volume, wherein the internal sizes capsule volume is free of The water sensitivity composition of gas can be produced when contacting at least one of liquid water and steam.

The another aspect of present disclosure is related to the capsule for delivering volatile composition, and the capsule includes: (a) packet Containing polyvinyl alcohol and limit the water-soluble glue softgel shell of internal capsule volume, in which: (i) described capsule shells have about 250 μm to about Wall thickness in the range of 3000 μm, and (ii) described capsule shells include pin hole, the pin hole is sized with shape to (A) It is allowed in gaseous fluid between the environment outside internal capsule volume and capsule shells to communicate, and (B) is limited in internal capsule and holds Liquid fluid communicates between long-pending and external environment；And the volatile compositions in internal capsule volume (b) are contained in, it is described to wave The volatile component of volatile compositions can be discharged in hair property composition in gaseous form.

The another aspect of present disclosure is related to a kind of product, comprising: (a) includes water-solubility membrane and limit small inside (i) The water-soluble pouch of bag volume and (ii) optionally pin hole, the pin hole are sized with shape to be allowed in inner pouch It is in fluid communication between environment outside volume and water-soluble pouch；(b) be contained in inner pouch volume according to each disclosure Aspect in capsule described in either segment, wherein water-soluble pouch includes pin hole (i) when capsule also includes pin hole, and (ii) the capsule shells pin hole (when it is present) and water-soluble pouch pin hole (when it is present) are in fluid communication；(c) in being contained in Laundry detergent composition in portion's pouch volume.

The another aspect of present disclosure is related to the method for washing clothing, which comprises (a) is in washing container Middle formation Aqueous wash medium, the Aqueous wash medium include (i) water, (ii) clothing, (iii) laundry detergent composition, (iv) capsule according to either segment in each disclosed aspect, wherein the composition includes cleaning combination；And (b) clothing is washed in Aqueous wash medium；Wherein until reaching selected until hydrotropism's liquid medium adds capsule Delay time washing cycle, cleaning combination just from capsule discharge.

The another aspect of present disclosure is related to the method for delayed release compositions into water-based liquid medium, described Method includes: that (a) provides the capsule according to either segment in each disclosed aspect, wherein the composition includes cleaning group Close object；(b) capsule is added to the water-based liquid medium comprising water；And dissolve capsule shells (c) to discharge cleaning combination to water Property liquid medium in, wherein until reaching selected delay time until hydrotropism's liquid medium adds capsule, cleaning combination Object is just discharged from capsule.

The another aspect of present disclosure is related to free-standing sustained release capsule, comprising: comprising water-soluble polymer and limits Surely the capsule shells of the inside capsule volume sealed, in which: (i) described capsule shells have in the range of about 100 μm to about 5000 μm Wall thickness, and (ii) described capsule shells have substantially homogeneous wall thickness.

The another aspect of present disclosure is related to the method for being used to prepare the capsule for sustained release delivering compositions, institute The method of stating includes: expectation composition of (a) selection for sustained release delivering；(b) expectation of the selection for sustained release delivering Aqueous medium condition, the aqueous medium condition include the temperature of the delayed release compositions aqueous medium to be delivered to, composition And stirring condition；(c) the expected delay time for the composition that selection will be discharged into aqueous medium；(d) selection wall thickness and Water-soluble polymer, so as to have the selected wall thickness of capsule shells, the water-soluble polymer of selected capsule shells and internal capsule The capsule of expectation composition in volume formed according to any of each disclosed aspect, until working as the capsule and having It is expected that the aqueous medium contact of aqueous medium condition and expected delay time for reaching, just composition it is expected in release；And (e) shape At the expectation combination having in the selected wall thickness of capsule shells, the water-soluble polymer of selected capsule shells and internal capsule volume The capsule according to any of each disclosed aspect of object.

The one aspect of present disclosure is related to the sustained release capsule for delivering water sensitivity composition, the capsule packet It includes: (a) including water-soluble polymer and the capsule shells for limiting internal capsule volume, in which: (i) described capsule shells have about 100 μ Wall thickness in the range of m to about 5000 μm, and (ii) described capsule shells include pin hole, the pin hole be sized with shape from And (A) is allowed in gaseous fluid between the environment outside internal capsule volume and capsule shells and communicates, and (B) is limited in internal sizes Liquid fluid communicates between capsule volume and external environment；(b) the water sensitivity composition being contained in internal capsule volume, it is described Water sensitivity composition can produce gas when contacting at least one of liquid water and steam.

The another aspect of present disclosure is related to the sustained release capsule for delivering water sensitivity composition, the capsule packet It includes: (a) including polyvinyl alcohol and the water-soluble glue softgel shell for limiting internal capsule volume, in which: (i) described capsule shells have about Wall thickness in the range of 250 μm to about 3000 μm, and (ii) described capsule shells include pin hole, the pin hole is sized and shape Shape is allowed in gaseous fluid between the environment outside internal capsule volume and capsule shells and communicates to (A), and in (B) be limited in Liquid fluid communicates between portion's capsule volume and external environment；(b) the water sensitivity composition being contained in internal capsule volume, institute Hydrogen peroxide gas can be generated when contacting at least one of liquid water and steam by stating water sensitivity composition (i), and And (ii) include selected from carbonate, borate, phosphate, sulfate, silicate, percarbonate, perborate, perphosphate, Inorganic bleaching agents in the group of persulfate, persilicate and their combination composition；Optionally (c) is contained in internal capsule At least one of bleach-activating and bleaching catalyst in volume.

In the particular refinement scheme of various capsule embodiments, capsule shells can have substantially homogeneous wall thickness.For example, institute The local thickness in substantially cross over the average wall thickness of entire capsule shells about 50% can be had by stating capsule shell wall.

The another aspect of present disclosure is related to a kind of product, comprising: (a) includes water-solubility membrane and limit small inside (i) Bag volume and (ii) pin hole water-soluble pouch, the pin hole be sized with shape to be allowed in inner pouch volume with Fluid (for example, gas or gas and liquid) communicates between environment outside water-soluble pouch；(b) it is contained in inner pouch appearance The sustained release capsule according to any of various disclosed embodiments in product, wherein capsule shells pin hole and water-soluble pouch Pin hole is in fluid communication；(c) detergent composition being contained in inner pouch volume is (for example, laundry detergent composition, wash Dishes detergent composition or other detergent compositions).

The another aspect of present disclosure is related to the method for washing clothing, which comprises (a) is in washing container Middle formation Aqueous wash medium, the Aqueous wash medium include (i) water, (ii) clothing, (iii) laundry detergent composition, (iv) according to the sustained release capsules of any of various disclosed embodiments, wherein the water sensitivity composition includes nothing Machine bleach compositions；(c) clothing is washed in Aqueous wash medium, wherein until reaching washing at least about 10 minutes Cycle delay time, the water sensitivity composition are just discharged into Aqueous wash medium from the capsule.In a refinement scheme In, sustained release capsule and laundry detergent composition can combine, such as according to any of various disclosed embodiments Water-soluble pouch product form, hydrotropism's washing medium provide.

The another aspect of present disclosure is related to the side for sustained release water sensitivity composition into water-based liquid medium Method, which comprises (a) provides the sustained release capsule according to any of various disclosed embodiments, wherein described Water sensitivity composition include cleaning combination (e.g., including individual inorganic bleaching agents, or with bleach-activating and/or bleaching The inorganic bleaching agents of catalyst combination)；(b) capsule is added to the water-based liquid medium comprising water；And (c) dissolution capsule shells with Cleaning combination is discharged into water-based liquid medium, wherein until reaching selected until hydrotropism's liquid medium adds capsule Delay time, the cleaning combination is just discharged into water-based liquid medium from the capsule.

According to the discussion being described below in detail with attached drawing, other aspects and advantage will for those of ordinary skill in the art It is obvious.Although composition and method allow various forms of embodiments, description hereafter includes specific real Apply mode, it should be understood that present disclosure is illustrative, and is not intended to and limits the invention to specific embodiments described herein.

Detailed description of the invention

Various disclosed methods, process, composition and product it is described in detail below referring to attached drawing, in which:

Fig. 1 is the sectional view for delivering the sustained release capsule of the water sensitivity composition according to present disclosure.

Fig. 2 be for aqueous delivery with according to the water-soluble of the sustained release capsule of another combination of compositions of present disclosure The sectional view of the small bag product of property.

Fig. 3 is an embodiment according to the sustained release capsule shells with substantially homogeneous wall thickness of present disclosure Sectional view.

Fig. 4 is another embodiment according to the sustained release capsule shells with substantially homogeneous wall thickness of present disclosure Sectional view.

Fig. 5 is another embodiment according to the sustained release capsule shells with substantially homogeneous wall thickness of present disclosure Sectional view.

Fig. 6 is the side section view according to the sustained release capsule for delivering numerous compositions of the other aspect of the disclosure Figure.

Fig. 7 is the sectional view according to the sustained release capsule for delivering compositions of the another aspect of the disclosure.

Specific embodiment

Delivering pouch and use disclosed herein is the capsule for the ingredient being contained therein for sustained release, comprising the capsule In using capsule (for example, to provide sustained release inorganic bleaching agents or other cleaning combinations into aqueous laundry washing medium) Correlation technique.

In order to realize sustained release of the alkaline components in washing cycle, water-solubility membrane parcel must be slowly dissolved and Keep substantially complete at nominal 40 DEG C in 15~20 minutes.It must also make the component mutual chemical phase of the small packet system of unit dose Perhaps mutual chemical isolation is to prevent from occurring with packaging material any chemically or physically changing.

Some water-soluble polymer films of parcel are used to prepare during this laundry wash period by endless fully dissolved, film Residue stays on the article in cleaning solution, or by Premature disintegration, causes to become unstable in the presence of other activating agents The effect of certain laundry additive (for example, enzymes), declines.

Water-soluble polymer films based on PVOH can undergo the change of dissolution characteristics.It is known to those skilled in the art to be copolymerized Acetate group in (vinyl acetate-ethylene alcohol) polymer can be hydrolyzed by acid or basic hydrolysis.When degree of hydrolysis increases, The polymer composition made of PVOH homopolymer resin will have increased mechanical strength but have reduction at a lower temperature Solubility (for example, it is desired to for be completely dissolved hot water temperature).Therefore, PVOH homopolymer resin is exposed to alkaline environment (for example, being caused by laundry bleaching additive) can by resin from be quickly and completely dissolved in given aqueous environments (for example, cold water be situated between Matter) one of type be converted into slow and/or be not exclusively dissolved in one of aqueous environments type, may be in washing cycle At the end of generate undissolved polymer residues.Be based only upon by business PVOH homopolymer resin represent vinyl acetate/ This in the application of the film of alcohol copolymer is an intrinsic weakness.

PVOH copolymer resin (such as vinyl alcohol/hydrolysis methyl acrylate sodium salt resin) with side position carboxyl, can Lactonic ring is formed between adjacent side position carboxyl and alcohol radical, thus reduces the water solubility of PVOH copolymer resin.Such as washing In the presence of the highly basic of clothing bleaching additive, lactonic ring can be opened in relative warmth (ambient enviroment) and high humidity (for example, logical Lactonic ring-opening reaction is crossed to form the corresponding side position carboxyl and alcohol radical with increased water solubility), last the mistake of several weeks Journey.Therefore, with the effect observed for PVOH homopolymer film on the contrary, it is believed that alkalinity during storage in film and pouch Chemical interaction between composition, this PVOH copolymer film can become more soluble.Therefore, small with their agings Packet can become increasingly easy Premature disintegration during (nominal 40 DEG C) of hot washing cycle, and can due to bleaching agent presence and The effect of generated pH influences then reduces certain laundry ingredients.

For delivering the water solubility/reactivity/dispersible pouch for the bleaching agent that there is delay relative to laundry detergent compositions The state of the art with parcel includes use multi-compartment water-soluble pouch made of polyvinyl alcohol (PVOH) film, wherein including solid The second pouch dissolve slower than the first pouch, such as in U.S. Patent No. 6,727,215 and U.S. Patent Bulletin the 2009/th Described in No. 0011970 and No. 2010/0192086.In addition, the various differences applied to the powder of bleaching agent or bleach-activating Immersion coating be described in U.S. Patent No. 4,725,378 as the mode of sustained release；No. 5,965,505；With 5,755, In No. 992.

(multiple) pin hole can be incorporated by film surface with the commercial product for delivering sodium carbonate and SODIUM PERCARBONATE using PVOH film In to allow gas to escape and keep the environmental pressure in pouch.This is usually alert stage, because SODIUM PERCARBONATE can produce oxygen The hydrogen peroxide that gas is generated as decomposition when the environmental condition of SODIUM PERCARBONATE and water or humid air and relative warmth contacts By-product.Pin hole can change to relatively large pin hole from lesser pin hole (diameter is micron) in about 1mm diameter.However, Known does not include that there is the commercial product of the PVOH of pin hole to attempt the inorganic drift of sustained release in the application of nominal 40 DEG C of water washings White agent material.

Fig. 1 show for deliver according to the water sensitivity composition 300 of the disclosure (for example, individual inorganic bleaching agents, or The inorganic bleaching agents combined with bleach-activating and/or bleaching catalyst) sustained release capsule 100.Capsule 100 includes limiting The capsule shells 200 of internal capsule volume 250, water sensitivity composition 300 are contained in the internal capsule volume.Capsule shells 200 Compatibly formed by water-soluble polymer composition as described below.As shown, capsule shells 200 include the first right shell element 210 (for example, the crown members for being equivalent to exemplary capsule filling and closure application) and the second left housing element 220 are (for example, be equivalent to The base member of exemplary capsule filling and closure application), both compatibly by water-soluble polymer composition (for example, identical Or different polymer compositions) formed, and usually cylindrical, there is hemispherical shell at one end.Shell element 210, it 220 is sized with shape so that they cooperate together in seal interface 215 (for example, along their cylindrical shaft Line) to limit capsule shells 200 and internal capsule volume 250 jointly.Capsule shells 200 have wall thickness T, suitably in about 100 μ In the range of m to about 5000 μm.Optionally, thickness T is basically uniform in entire capsule shells 200.Optionally, thickness T It can be used as the function variation of position, such as the overlapping based on shell element 210,220 is (for example, such as thickness T₁It is shown) and/or be based on Specific manufacturing method is (for example, such as end wall thickness T₂It is shown, T₂It can be different from side thickness shown in T as shown in figure 1).

Capsule shells 200 include pin hole 240.In the embodiment shown, pin hole 240 is located at the half of first shell element 220 In spherical substrate.In other embodiments, pin hole 240 can be located in any or multiple shell elements 210,220 (for example, working as glue When softgel shell 200 includes multiple pin holes 240).Similarly, pin hole 240 can be located at capsule shells 200 on random desired location (for example, End wall, side wall) at.Show that pin hole 240 has diameter D (for example, indicating the round round diameter of pin hole or the water of non-circular pin hole Power diameter (D_H)) and length L (for example, the wall thickness T for corresponding to the capsule shells 200 of the part near pin hole 240).Pin hole 240 It is sized with shape to allow environment E of the gas outside internal capsule volume 250 and capsule shells 200_cBetween fluid phase It is logical.Therefore the permission of pin hole 240 is discharged by any gas that water sensitivity composition 300 generates from capsule shells 200 after contact with water, And shell 200 is without apparent pressure build-up and/or damage or deformation.Although gaseous fluid is allowed to communicate, pin hole 240 is set Size and shape is determined so that internal capsule volume 250 and external environment E is restricted or prevented_CBetween liquid fluid communicate.Thus pin hole 240 prevent liquid water from entering internal capsule volume 250, such as when capsule 100 is placed in water-based liquid medium (that is, preventing from prolonging Liquid enters until water-based liquid medium finally dissolves capsule shells 200 and arrived with discharging water sensitivity composition 300 during slow time window In medium).

Fig. 2 shows the products of the capsule 100 combined with another composition 460 for aqueous delivery, especially wherein glue The delivering of the content 300 of capsule 100 will postpone relative to composition 460.In a kind of embodiment, capsule 100 includes independent Inorganic bleaching agents, or inorganic bleaching agents combined with bleach-activating and/or bleaching catalyst, as its water sensitivity composition 300, and composition 460 includes one or more laundry compositions, such as detergent, fabric softener, bleach-activating, drift White catalyst etc. (for example, bleach-activating and bleaching catalyst independently can be combined or be separated with inorganic bleaching agents).In Fig. 2 In, water-soluble pouch 400 is formed by water-solubility membrane 410 (for example, cold water soluble film), shows that it has first (or top) film Element 412 and second (or bottom) membrane component 414.Membrane component 412,414 is sealed (for example, heat seal and/or solution sealing) To limit the inner pouch volume 450 for including capsule 100 and composition 460.Water-solubility membrane 410 includes pin hole 440, the pin hole It is sized the environment E with shape to be allowed in outside inner pouch volume 450 and water-soluble pouch 400_PBetween fluid phase It is logical.Pouch pin hole 440 can with the same size of shell pin hole 240, but its be not required to resist liquid fluid communicate, because of water-solubility membrane 410 than the relatively rapid dissolution of capsule 100, and capsule 100 provides the big of any sustained release property of water sensitivity composition 300 Measure the duration.

Capsule 100 is arranged in inner pouch volume 450 so that its pin hole 240 and 440 fluid phase of water-soluble pouch pin hole It is logical.This be allowed in the gas generated in internal capsule volume 250 lead to inner pouch volume 450 (or, equally, outer capsule Environment E_C) in and then lead to outer pouch environment E_PIn.As shown in Figure 2, film 410 can be shaped and be sealed in offer The first compartment 452 and second compartment 454 of the physical separation of portion's pouch volume 450.First compartment 452 limits pouch pin hole 440 And include capsule 100, and second compartment 454 include composition 460 and compatibly not with pouch pin hole 440 or outer pouch ring Border E_PIt is in fluid communication.

Using capsule and capsules sachets can be contained in the method for washing clothing.By by water, clothing, laundry composition (for example, detergent) and according to the capsule combination of present disclosure and including inorganic bleaching agents composition, cleaning combination or Other compositions are initially formed Aqueous wash medium in washing container.Can by washing medium component with any desired order and With any desired relative quantity (e.g., including according to the type of clothing to be washed and amount correspond to manufacturer specification relative quantity Water, detergent and inorganic bleaching agents or other compositions) to conventional washing machine add.Suitably, described herein above water-soluble Property small bag product form combination addition capsule and laundry composition.Then, usually with any appropriate selected wash time With temperature (for example, about 30 minutes or 45 minutes to about 60 minutes or 75 minutes washing cycles, optionally followed by about 10 minutes or 20 minutes to about 30 minutes or 40 minutes rinse cycles；About 20 DEG C, 40 DEG C or 60 DEG C of wash temperature) in Aqueous wash medium Middle washing clothing.While washing, capsule sustained release inorganic bleaching agents composition or other compositions are situated between to Aqueous wash Until reaching at least about 10 minutes delay times washing cycle (for example, from capsule or containing capsules sachets and aqueous medium group in matter The time of conjunction measures).In various embodiments, delay time washing cycle can be at least about 10 minutes, 12 minutes, 14 minutes Or 15 minutes and/or long of about 14 minutes, 16 minutes, 18 minutes, 20 minutes or 25 minutes.Optionally or additionally, it may be selected to wash It washs the cycle delay time (for example, based on selection capsule thickness of the shell, capsule shells water-soluble polymer composition, and/or expected washing Condition) so that it is short enough so that it is guaranteed that in starting (or cleaning) period before subsequent draining event and/or rinse cycle Period, release capsule content was into Aqueous wash medium.Similarly, delay time washing cycle may be selected so that its long enough So that it is guaranteed that early stage clean cycle and draining event (for example, wherein water, the detergent being finished, removal laundry soil etc. from Container discharge is washed, and the clothing that cleaned and not yet dissolved gum capsule stay and are used for subsequent rinse cycle in a reservoir) after Rinse cycle during release capsule content into aqueous rinse medium.Sustained release is to exist until the benefit of rinse cycle Reduced levels from Aqueous wash medium (for example, surfactant, antiredeposition auxiliary agent etc.) are (for example, be not present or substantially On be not present) detergent or other cleaning combinations to be mixed by capsule delivery and with clothing or the specific group that contacts with transporting It closes object (for example, wherein capsule composition is ideally deposited in some cases on clothes or other clothings).Suitable for rinsing The period exemplified composition of release includes softening agent (for example, it can adversely be contacted with many detergent) and essence (for example, leading Cause the effective yield of the essence stayed on clothing after washing higher).(for example, in washing cycle and rinsing at the end of washing After any one of period or both), the visible residue (example that clothing is generated without the endless fully dissolved due to capsule shells Such as, through visually inspecting).

It more generally, can be for sustained release water sensitivity or other composition in method into water-based liquid medium Using capsule and contain capsules sachets.It will be according to present disclosure and including cleaning combination (for example, independent or and bleach-activating And/or bleaching catalyst combination laundry or dishwashing composition, such as inorganic bleaching agents) capsule be added to first including water Water-based liquid medium.On the one hand, water-based liquid medium can be to be formed by component as described above and including as described above group The aqueous laundry of (for example, further comprising clothing and laundry detergent composition, wherein capsule includes inorganic bleaching agents) is divided to wash Wash medium.On the other hand, water-based liquid medium can be aqueous dishwashing medium, for example, further including dishwashing in addition to capsule Detergent composition (for example, its may include in inorganic bleaching agents and/or another sustained release dishwashing additive wherein, Such as rinse aid).For example, aqueous dishwashing medium can conventional warewashing machines wash container sink in formed (for example, By directly adding capsule to washing container, or by after starting washing cycle or washing cycle predefined phase by glue Capsule is discharged into the compartment addition capsule in washing container).Dishwashing medium follows in entirely washing container during washing cycle Ring (for example, the spraying machine and gravity using pump driving recycle) is to contact and clean the tableware being contained in washing container (for example, dishes, glassware, silverware, kitchen utensils, cooker and other tablewares).Suitably, capsule and detergent composition (for example, laundry detergent composition, dishwashing detergent composition) combination, example water-soluble pouch product as described above (for example, Detergent composition is in a pouch compartment and capsule is in another pouch compartment) form hydrotropism's liquid medium addition. Then, usually with any appropriate selected time and temperature (for example, in washing cycle, for example, about 30 minutes or 45 minutes To laundries in about 60 minutes or 75 minutes or dishwashing washing cycle, optionally followed by about 10 minutes or 20 minutes to about 30 minutes Or 40 minutes rinse cycles；About 20 DEG C, 40 DEG C or 60 DEG C of wash temperature) by capsule shells be dissolved in water-based liquid medium with Cleaning combination is discharged into water-based liquid medium.During dissolution, capsule sustained release cleaning combination to waterborne liquid is situated between Reach selected delay time (for example, can wherein be based on capsule wall until hydrotropism's liquid medium adds capsule in matter Thickness is that one group of given water-based liquid medium condition selects the expected delay time).In various aspects, delay time can be at least about 10 minutes, 12 minutes, 14 minutes or 15 minutes and/or long of about 14 minutes, 16 minutes, 18 minutes, 20 minutes or 25 minutes.? (for example, in any of washing cycle and rinse cycle at the end of the cleaning frequency that capsule is used for sustained release cleaning combination Person or both is rear), the article (for example, clothing, tableware) cleaned is free of the endless fully dissolved due to capsule shells and generates Visible residue (for example, through visually inspecting).

Disclosed capsule can be designed and be manufactured according to the expected delay release characteristic of composition.It is being used to prepare basis In the method for the sustained release capsule of present disclosure, interested sustained release is applied and limited according to following: (i) is for prolonging The expectation aqueous medium and (iii) that expectation composition that slowbreak is put, (ii) composition to be delivered to will be discharged into aqueous medium In composition the expected delay time (or acceptable delay time range).Aqueous medium can further be limited according to following It is fixed: one or more conditions of the aqueous medium of the dissolving characteristic of the capsule according to present disclosure to be influenced, for example including aqueous The temperature of medium, aqueous medium composition (for example, its component in addition to water, such as each disclosed laundry or its Detergent or other cleaning combinations in its Cleaning application)；And/or the stirring of aqueous medium with capsule (for example, when connecing When touching, whether aqueous medium stirs and how to stir or mix in other ways).In view of the application of interested sustained release Limit, then combine selection for wall thickness and the specific water soluble polymer composition of capsule shells so that with (i) selected wall thickness, (ii) the expectation composition that the water-soluble polymer composition and (iii) selected are contained therein is formed according to present disclosure Capsule, until the capsule being thusly-formed contacts and expected delay time for reaching just discharges expectation composition with aqueous medium. For example, water-soluble polymer can be selected according to any easy standard, for example, with the chemical compatibility of it is expected composition, manufacture Easness and/or cost etc..In view of selected water-soluble polymer, then it can therefore select shell wall thickness to provide at aqueous medium In the expected delay time (for example, the aqueous medium condition given for one group, wherein thicker wall generally correspond to it is longer Dissolution or release time, vice versa).

Unless otherwise stated, expected disclosed capsule, delivering pouch comprising capsule and associated method include Including in the other optional element, feature and step (including those shown in drawings and examples) that are discussed further below One or more any combination embodiment.

In any embodiment, capsule and/or water-soluble pouch may be included in composition (the generally water-sensitive in capsule Property composition) and different components in pouch.Composition can be selected from liquid, solid or their combination.Such as this paper institute It uses, " liquid " includes the fluid and dextrin, gel, foam and mousse (mousses) flowed freely.The non-limit of liquid Property example processed includes light-duty and heavy duty liquid laundry detergent composition, fabric intensifier, the detergent gels for being usually used in laundry, bleaching Agent and laundry additive.Gas (such as suspended bubble) or solid (such as particle) may include in the liquid.Such as this paper institute " solid " used includes but is not limited to powder, aggregate and their mixture.The non-limiting example of solid includes: Grain, microcapsules, bead, bar and pearly-lustre ball.Solid composite can provide process benefit, including but not limited to, thoroughly wash Benefit, pretreatment benefit and/or aesthetic effect.

For example, composition can be selected from the light dirt of liquid and liquid the heavy scale liquid in the embodiment arbitrarily centered on doing washing Body detergent composition, powder detergent composition, fabric intensifier, the detergent gels and bleaching agent (example for being usually used in laundry Such as, organic or inorganic bleaching agent) and the group of laundry additive in.

As used herein, " gaseous fluid relevant to the pin hole in capsule shells and/or the water-soluble pouch of closed capsule Communicate " it indicates to be sized to allow the opening across Convective and diffusivity the gaseous mass transport of pinhole boundary.Although Capsule and pouch disclosed herein can by vulnerable to gaseous matter across they solid boundaries diffusivity mass transportation to they In internal capacity and/or be transported out they internal capacity influence material formed, but it is such transport be different from pin hole held Perhaps gaseous fluid communicates.

As used herein, term " homopolymer " generally includes the polymer of the monomeric repeating unit with single type (for example, by or substantially the polymer chain that is made of single monomer repetitive unit).For the concrete condition of PVOH, term is " Polymers " (or " PVOH homopolymer ") further comprises (taking with vinyl alcohol monomer units and vinyl acetate monomer units distribution Certainly in degree of hydrolysis) copolymer (for example, polymer chain by or be substantially made of vinyl alcohol and vinyl acetate monomer units). In the limiting case of 100% hydrolysis, PVOH homopolymer may include real homopolymer only with vinyl alcohol units.

As used herein, term " copolymer " generally includes the monomeric repeating unit with two or more seed types Polymer (for example, by or substantially be made of two or more different monomers repetitive units (no matter as random copolymer, Block copolymer etc.) polymer chain).For the concrete condition of PVOH, term " copolymer " (or " PVOH copolymer ") is into one Step include with vinyl alcohol monomer units and vinyl acetate monomer units distribution (depend on degree of hydrolysis) and it is at least one its The monomeric repeating unit of its type copolymer (for example, by or substantially by vinyl alcohol monomer units, vinyl acetate monomer list Three (or more) polymer chain) of first and one or more of the other monomeric unit composition.In the limiting case of 100% hydrolysis, PVOH copolymer may include but being total to without vinyl acetate unit with vinyl alcohol units and one or more of the other monomeric unit Polymers.

As used herein, the instruction of term "comprising" may also include other reagents, member other than those of specified Part, step or feature.

As used herein and unless otherwise stated, term " wt.% " and " wt% " mean with the weight of entire film Part in terms of " drying " (non-aqueous) part (as applicable) of meter or the weight of the entire composition to be encapsulated in pouch is (when applicable When) identification element composition.As used herein and unless otherwise stated, term " phr " means in water-solubility membrane often 100 parts of water-soluble polymers (or resin；No matter PVOH or other) number identification element composition.

All ranges set forth herein includes any combination of all possible range subset He these subset ranges.Unless It is otherwise noted, otherwise by default, these ranges include the endpoint.When providing the range of value, it should be appreciated that at this Each median between the upper and lower bound of range and any other value or median in the range In present disclosure.These small range of upper and lower bounds can be independently include in smaller range, and also be wrapped It is contained in present disclosure, arbitrarily is clearly excluded to be limited by the range.When the range includes one or two When limit value, the range for excluding either one or two of limit value that those include also is thought of as a part of this disclosure.

Capsule shells

Described in Fig. 1 and the capsule shells 200 above substantially described are influenced vulnerable to various refinement schemes and embodiment.

Capsule 100 and shell 200 are set appropriately size with the water sensitivity combination being contained therein comprising unit dose Object 300.For example, internal capsule volume 250 can be in the range of about 0.1ml to about 100ml (for example, more generally at least about 0.1ml, 1ml, 5ml, 10ml or 15ml and/or be up to about 10ml, 15ml, 20ml, 30ml, 50ml or 100ml).Optionally, right The laundry applications (for example, to deliver inorganic bleaching agents) described in embodiment as described herein and as follows, in addition to just describing Those of except value and range, internal capsule volume 250 can be in the range of about 5ml or 10ml to about 30ml or 50ml.It is optional Ground or in addition, the size of shell 200 can be indicated according to characteristic length, such as minimum length and/or maximum length are (for example, general circle The diameter and height of cylindrical shell are as being respectively minimum and maximum, and aspect ratio (height/diameter) is greater than 1).(no matter most characteristic length It is small or maximum) it can be in the range of about 0.3cm to about 10cm.For example, feature minimum length can at least about 0.4cm, 1cm, 1.5cm, 2cm or 5cm and/or it is up to about 1.5cm, 2cm, 3cm, 5cm or 10cm.Similarly, feature maximum length is equal to or greatly In feature minimum length, and it can independently be selected as at least about 0.4cm, 1cm, 1.5cm, 2cm or 5cm and/or be up to about 1.5cm, 2cm, 3cm, 5cm or 10cm.On the one hand, feature minimum length optionally or additionally may be selected is made with being larger than The limitation size in the container middle outlet aperture of capsule 100 is added with period.For example, feature minimum length can be greater than in washing container Draining and/or recycling exit aperture, therefore keep capsule 100 inside washing vessel volume in until capsule dissolve and release Put capsule 's content (that is, because capsule 100 is too big when still complete and proper drainage or recycling behaviour when cannot pass through washing Make from the removal of inside washing vessel volume).In such embodiment, feature minimum length may be, for example, at least 0.4cm or extremely Few 0.5cm or at least 0.6cm or at least 0.7cm or at least 1cm.

As described above, pin hole 240 is sized with shape to which (i) is allowed in internal capsule volume 250 and capsule shells Environment E outside 200_CBetween gaseous fluid communicate, and (ii) is restricted or prevented in internal capsule volume 250 and external rings Border E_CBetween liquid fluid communicate.By the inclusion of one or more pin holes 240 in capsule shells 200, what capsule 100 allowed to generate Sustained release property of the gas evolution without damaging the heavy wall construction offer by capsule 100.Pin hole 240 can have about 10 μm in the range of about 1500 μm (for example, more generally at least about 10 μm, 50 μm, 100 μm, 200 μm or 500 μm and/or high Of about 100 μm, 200 μm, 500 μm, 1000 μm or 1500 μm) diameter (D；Cylindrical diameter or Equivalent Hydraulic Diameter), for example, To provide effective water penetration barrier, while allowing the internal gas evolution generated.Suitable aperture size is optionally or additionally It may be expressed as ratio of the capsule wall thickness (that is, the length L in 240 channel of pin hole) relative to the diameter D of pin hole 240.In general, capsule Shell wall thickness T or passage length L are smaller, and it is straight to be suitable for the pin hole that liquid (gas-vs.-liquid) is selectively in fluid communication in gas Diameter D is smaller, and vice versa.For example, pin hole 240 can have such length (L) and diameter (D), corresponding L/D ratio is about In the range of 0.2 or 1 to about 5,10 or 100 0.01, (for example, more generally at least about 0.01,0.1,0.2,0.5 or 1 and/ Or up to 1,2,5,10,20,50 or 100).

Other than the specially suitable sizes values of pin hole 240 described above, the various desired functions based on capsule 100 The size of pin hole 240 in specific application may be selected in property.For example, may be selected pin hole length (L), size or diameter (D) and/or Ratio L/D so that it/they correspond to the size of the particle that is contained in capsule or powder water sensitivity or other compositions 300 Sufficiently small, thus prevent 300 particle of composition escaped during storage or aqueous media add capsule after too early Evolution.Additionally or alternatively, pin hole 240 can be sufficiently large/short to promote the gas generated quickly to escape into external environment (example Such as, prevent air accumulation and relative physics capsule 100 from damaging).Similarly, pin hole 240 can be sufficiently small/long in allusion quotation (for example, pressure and temperature under type laundry situation；Such as water or water substance in liquid water or aqueous laundry washed mixture Viscosity and density in terms of) liquid be restricted or prevented lead to internal capsule volume from external environment.

Pin hole 240 can be incorporated in any suitable manner in capsule shell structure 200.As be shown in the examples, pass through The needle-penetration shell 200 of desired specification is used after having formed basic 200 structure of shell, to add pin hole 240 to capsule shells 200.? In another embodiment, capsule shells 200 may include the pin hole 240 as originally formed.For example, limiting one or more shells 200 The mold of the expectation wall geometry of component may include 240 element of pin hole, to form pin hole 240 during molding.

It can be based on the expected delay time (for example, minimum value, maximum value or range) for discharging water sensitivity composition 300 And/or shell 200 is dissolved completely in the maximum duration of the capsule in its dissolution medium, selects capsule shells 200 in a given application Wall thickness T.For example, wall thickness can be in the range of about 100 μm or 250 μm to about 1500 μm or 5000 μm (for example, being more generally At least about 100 μm, 200 μm, 250 μm, 500 μm, 750 μm or 1000 μm and/or be up to about 1000 μm, 1250 μm, 1500 μm, 2500 μm, 2500 μm, 3800 μm or 5000 μm；At least about 5 mils, 8 mils, 10 mils, 20 mils, 30 mils or 40 mils And/or be up to about 40 mils, 50 mils, 60 mils, 80 mils, 100 mils, 150 mils or 200 mils approximate mil it is equivalent Range).Suitable wall thickness range for various applications example (for example, the aqueous solution temperature of typical case based on given application, The expected delay time of composition and stirring capsule exposure condition) can include: about 100 μm or 200 μm to about 500 μm or 750 μm, About 250 μm or 500 μm to about 750 μm or 1000 μm, about 750 μm or 1000 μm to about 1500 μm or 2000 μm, about 1000 μm or 1500 μm to about 2000 μm or 2500 μm or about 2000 μm or 2500 μm to about 3800 μm or 5000 μm.Minimum value above-mentioned, most Big value and range are suitble to suitable for such capsule, and the capsule is intended for delivering the nothing in laundry applications as described herein Machine bleaching agent, cleaning combination and other compositions.Disclosed wall thickness value and range can indicate substantially across capsule shells 200 Whole surface capsule shells 200 average (such as average surface area) thickness and/or capsule shells 200 local thickness's value.? In the case that the shell element of two or more cooperations limits capsule shells 200 jointly, the shell element of cooperation can meet entirety jointly Capsule shells property (for example, such as wall thickness, average wall thickness, wall uniformity).

Capsule shells 200 shown in Fig. 1 usually have wall thickness T；However, due to the superimposed structure at seal interface 215, Shell 200 has by T₁Some regions of the non-uniform thickness of expression.It is as follows as described in the examples, there is a degree of wall Advantageous sustained release and dissolution properties can be presented in thick heteropical capsule 100

In other embodiments, capsule shells 200 can be configured to have substantially homogeneous wall thickness T.Substantially homogeneous wall Thick T can promote the uniform complete disintegration of capsule shells 200.The uniformity of total wall thickness also contributes to limiting undissolved capsule shells 200 polymer are subjected to the degree for the corrosivity alkaline environment that can be generated when finally releasing water sensitivity composition 300.For portion Divide the concrete condition of the PVOH of hydrolysis, undissolved PVOH resin can further be hydrolyzed by being exposed to alkaline environment, make it relatively more Insoluble (especially in cold water), and generate the residue that can for example retain in laundry wash end cycle.Wall thickness it is equal Even property allows capsule wall dissolution and thinning in an uniform way, so as to discharge in the last disintegration of capsule shells 100 and composition 300 Afterwards, the wall thickness of any 200 element of remaining shell is as thin as possible, so that undissolved fluoropolymer resin be made to be exposed to corrosive environment Weight minimize.Uniform dissolution also increases the surface to volume ratio of any remaining capsule shell polymeric, this makes It is more likely to be completely dissolved (no matter for example, capsule 's content) during washing cycle.Substantially homogeneous wall thickness further promotees Into the consistency (for example, water sensitivity or other aspects) in the release time (or release profiles) of any particular composition 300, because Tend under consistent washing or other dissolution conditions substantially discharge in its whole under consistent wash time for capsule 100 It is tolerant.

The feature of significant wall uniformity can be, for example, substantially crossing over the average wall thickness of entire capsule shells 200 Local thickness T (for example, with average wall thickness of surface area weight) in about 50%.More specifically, local thickness T can be in mean wall In about 1% thick, 2%, 5%, 10%, 20%, 30%, 40% or 50%, for example, as across at least 80%, 90%, 95%, The surface area measurement of 98% or 99% external shell 200.On the other hand, the feature of wall uniformity can be in release content The substantially uniform dissolution of capsule shells 200 before object, for example, the shell matter of wherein at least 80%, 90%, 95%, 98% or 99% It is dissolved before release water sensitivity or other compositions 300

Fig. 3~5 elaborate 200 embodiment of alternative capsule shells with substantially homogeneous wall thickness T.

Similar with the embodiment of Fig. 1 in Fig. 3, capsule shells 200 include first shell element 210 and second shell element 220, it is fitted to each other during manufacture shell 200 is collectively formed.As shown, in the hemispherical end wall of shell element 210,220 The wall thickness at place be shell element 210,220 sidewall areas wall thickness approximately twice as.Sidewall areas with half end wall thickness is filled Seal area between element 210,220.Once two shell elements 210,220 are combined together at seal interface 215, side wall The thickness in region is just combined to form wall thickness identical with the wall thickness at end wall, to generate uniform in having for its assembling form Wall thickness T capsule shells 200.

The embodiment of Fig. 4 and the embodiment of Fig. 3 are similar, because of the side of the capsule shells element 210,220 of capsule shells 200 Wall region is thinner than corresponding endwall region.However, being not there is the side wall of uniform thickness, but side wall has as axial position The thickness of the function set to successively decrease, but complementary side wall common combination to be to form wall thickness identical with the wall thickness at end wall, thus Generate the capsule shells 200 with uniform wall thickness T in its assembling form.

Fig. 5 elaborates another embodiment, and wherein capsule shells 200 by limiting the uniform wall thickness T's in assembly shell 200 jointly Multiple formation of shell element 210,220,230.In Fig. 5, the first and second shell elements 210,220 have the embodiment such as Fig. 3 In relatively thin sidewall areas, but they are cooperated in assembling shell by third cylinder inner housing member 230.For example, It is desired to have specifically and in the embodiment on the interior lining surface of the chemical compatibility of water sensitivity composition 300, inner casing member Part 230 can be by forming with the identical or different water-soluble polymer composition of shell element 210,220.

Other than providing uniform wall thickness, another advantage of the embodiment of Fig. 3~5 is that they provide the height of seal area Contact surface area, it is ensured that assembly capsule 100 in fluid-tight sealing.Capsule shells 200 can pass through the high surface of sealing area Long-pending frictional force, using water (or other sealing solution) or using allow shell element 210,220 once couple be locked in together and Do not damage water-tight seal surface elevation or protrusion (not shown) and seal.In addition, if solution (such as water, or including water) It is used for solution capsul element 210,220, then it can be applied in this way: remote enough from water sensitivity composition 300 To prevent any unexpected interaction with it (that is, wherein composition 300 will exist inside capsule volume in sealing In 250, even if being not illustrated in Fig. 3~5).

Such as being further displayed in Fig. 3~5, pin hole 240 can be placed in first (or " top ") shell element 210, rather than Second (or " bottom ") shell element 220 as shown in Figure 1 (or in addition)." top " and " bottom " shell element 210,220 Be the relative terms for reflecting the mode for actually assembling capsule 100: water sensitivity or other compositions 300 are placed in second (bottom) In shell element 220, then first (top) shell element 210 slidably mate in the axial direction with second (bottom) shell element 220 with The composition 300 that two elements 210,220 are sealed and defines assembly capsule 100 and is contained therein.When first When (top) element 210 is crushed on second (bottom) element 220, placement of the pin hole 240 in first (top) shell element 210 Air is allowed to escape in manufacture/period of assembly.Which increase the easiness and speed of producible capsule 200, and avoid Internal pressurization of the manufacture/period of assembly to capsule 100.

Although describing capsule 100 shown in Fig. 1 and 2,100 He of capsule with specific reference to water sensitivity composition 300 The composition 300 for including in shell 200 more generally may include one or more other ingredients, including various cleanings as described herein Composition (no matter for example, water sensitivity, production gas in the absence of water or exhaust, or other means).More generally, when When composition 300 is into gas composition 300, pin hole 240 is used to allow to produce by the composition 300 in internal capsule volume 250 Gas external environment E raw or being discharged from it_CEvolution, and though gas whether to water haptoreaction and formed (for example, logical Gas composition 300 is crossed into be reacted with water to discharge the gas for generating gas and generating), whether gas contacts to the substance for not being water It reacts and forms (gas generated and for example, generating gas by reacting at gas composition 300 with other materials to discharge), gas Whether formed in the case where water or other materials are not present (for example, being discharged from gas composition 300 without anti-with another component The gas answered, such as by discharging its volatile component), whether gas generation is desired etc..For example, at gas composition 300 It may include essence, essence gas can be discharged and pass through 240 slow release of pin hole.In addition, as described above, pin hole 240 in shell 200 Presence by allow gas (for example, air of headspace) from internal capsule volume 250 escape and promote capsule 100 fill Match, even if composition 300 does not form gas in storage or using during assembling capsule 100.

Fig. 6 is similar with Fig. 1, and it illustrates the capsules 100 including two kinds of compositions 300A, 300B, although capsule 100 It more generally may include any amount of different components (for example, wherein other (a variety of) in every kind of composition and capsule 100 Composition and with 200 material compatible of shell).The capsule 100 of Fig. 6 may be incorporated into as described above and in water solubility shown in Fig. 2 In pouch 400.Compatibly, at least one of composition 300A, 300B is that at gas composition and can generate or be discharged gas (for example, producing the water sensitivity composition of gas when contacting with liquid water and/or vapor, discharge is in the gas of its native state Air exhaust combination object, such as even in the case where liquid water and steam is not present), and in composition 300A, 300B extremely Few one kind is intended for the sustained release in aqueous environments.On the one hand, composition 300A be air exhaust combination object, can with or not It is expected that it is used for sustained release, and composition 300B to be cleaning or the laundry composition for being intended for sustained release, described group Close object can with or can not be at gas composition, gas-generating agent composition or air exhaust combination object.

For example, composition 300A can be volatile compositions, such as essence or spice composition, discharge is in its natural shape Its volatile component of state, such as essence gas is (for example, the volatility group of the essence combination of the smell with pleasant Point) (no matter for example, whether it contacts with water or in addition contact or react with another Enviromental pollutants).The presence of pin hole 240 The volatile component being discharged or essence gas is allowed to escape into outer capsule environment E_CWith outer pouch environment E_PIn (for example, working as glue When capsule 100 is incorporated in the water-soluble pouch 400 with corresponding pin hole 440).The essence gas of discharge is waved with what is in addition issued The evolution of hair property component is beneficial, because of its component frowzy that can cover capsule 100 and/or pouch 400, for example, To the storage container comprising multiple capsules 100 and/or pouch 400 (for example, case, box etc. during its storage；It is not shown) it provides The smell of pleasant.

On the one hand, composition 300B can be essence or other perfume compositions, not be discharged in its native state (example Such as, in its originally to capsule 100 provide in the form of) gas.For example, composition 300B may include essence or aroma constituent, Be coated or encapsulate so that composition 300B be not discharged substantially during storage its essence or aroma constituent (for example, coating or Encapsulating material prevent or be greatly decreased by gas essence or aroma constituent).This composition 300B can be used for laundry or Sustained release during other cleaning frequencies, for example, with during the cleaning frequency later period be introduced into Aqueous wash medium, to make It obtains composition and is attached to the article just cleaned.After cleaning frequency (and drying cycles, if applicable), composition 300B is protected Hold be attached to the article cleaned and delay/sustained release of essence or other fragrance smells that pleasant is provided (for example, The coating of composition 300B or encapsulating material finally rupture to discharge its essence or aroma constituent, such as in the article cleaned When wearing or during other uses).

Fig. 7 elaborates the alternate embodiments of the capsule 100 of the disclosure, and wherein capsule 100 and capsule shells 200 do not include needle Hole.Shell 200 defines the inside capsule volume 250 of sealing, to prevent the inside capsule volume 250 and outer capsule in sealing Environment E_CBetween gaseous fluid communicate.In some cases, composition 300 is not easy be bullied body formation or the reactive influence of water (for example, no matter in its native state or have reaction to surrounding material (such as water)).In these cases, sealing be free of needle The capsule 100 in hole still provides the benefit of the sustained release to its composition 300.Similarly, with embodiment party described in Fig. 3~5 The similar capsule 100 without pin hole of formula can be used for providing substantially homogeneous wall thickness T and its companion described above to shell 200 With dissolution, disintegration and/or releasing properties advantage.In some embodiments, it is possible to provide the capsule 100 without pin hole is independent Form (for example, with or without the composition being contained therein, for example, its hollow capsules be expected to it is open, filled with combination Object and re-closed or again seal).

Water-soluble polymer composition

Water-soluble polymer composition well known in the art, the optional component wherein used with and preparation method thereof, no Pipe is used to prepare the formation resin structure that water-solubility membrane relatively thin as is known (for example, such as sachet material) is still instructed herein Relatively thick water-solubility membrane, such as capsule (for example, as capsule material).

In a kind of embodiment, water-soluble polymer composition includes polyvinyl alcohol (PVOH), including its homopolymer (example Such as, including substantially only vinyl alcohol and vinyl acetate monomer units) and its copolymer (e.g., including in addition to vinyl alcohol and second One or more other monomeric units except vinyl acetate unit).PVOH is generally (logical by the alcoholysis of polyvinyl acetate Be commonly referred to as hydrolyze or be saponified) preparation synthetic resin.(wherein almost all of acetate group has been all by the PVOH of complete hydrolysis Be converted to alcohol radical) be strong hydrogen bonding bonding highly crystalline polymer, be only dissolved in the hot water of greater than about 140 °F (60 DEG C) In.If allowing (to keep sufficient amount of acetate group in polyvinyl acetate after hydrolysis, PVOH polymer is known as Partial hydrolysis, hydrogen bonding is weaker and crystallization is less, and dissolves in the cold water below about 50 °F (10 DEG C).Intermediate Cold or hot water solubility's polymer composition may include for example, the PVOH of intermediate partial hydrolysis is (for example, with about 94% to about 98% degree of hydrolysis), and can only be readily dissolved in warm water, for example, quickly being dissolved under about 40 DEG C or higher temperature.It is complete All-hydrolytic and the PVOH type of partial hydrolysis are commonly known as PVOH homopolymer, but the type of partial hydrolysis is academicly being ethylene Alcohol-vinyl acetate copolymer.

The degree of hydrolysis (DH) for being contained in the PVOH in the water-soluble polymer composition of the disclosure can be about 75% to about In the range of 99% (for example, about 79% to about 92%, about 86.5% to about 89% or about 88%, such as cold water soluble Composition).When degree of hydrolysis reduce when, polymer composition made of resin below about 20 DEG C at a temperature of will have reduction Mechanical strength but faster solubility.When degree of hydrolysis increases, the polymer composition made of polymer will physically Tend to be stronger, and hot-forming property will tend to decline.The degree of hydrolysis of PVOH be can choose so that the water solubility of polymer is temperature Spend dependence, therefore the solubility of the polymer composition made of polymer, any expanding material polymer and added ingredient Also impacted.In a kind of selection, polymer composition is cold water solubles.Lower than 10 DEG C at a temperature of it is water-soluble in Cold water soluble polymers composition may include degree of hydrolysis in the range of about 75% to about 90% or about 80% to about 90% In the range of or PVOH in the range of about 85% to about 90%.In another kind selection, polymer composition is that hot water can Molten.It may include that degree of hydrolysis is at least about at least about 60 DEG C of at a temperature of water-soluble hot water solubility's polymer composition 98% PVOH.

Other than PVOH or other water-soluble polymers used in the alternative solution of PVOH may include but be not limited to Modified polyvinylalcohol, polyacrylate, water-soluble acrylic ester copolymer, polyvinylpyrrolidone, polyethyleneimine, Pu Lu Blue sugar (pullulan), water-soluble natural polymer (including but not limited to guar gum, xanthan gum, carrageenan and starch), water Soluble polymer derivative (including but not limited to, ethoxylated starches and hydroxypropylated starch), copolymer above-mentioned and Any combination above-mentioned.Other water-soluble polymer may include polyalkylene oxide, polyacrylamide, polyacrylic acid and its salt, Cellulose, cellulose ether, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and its salt, polyaminoacid, polyamides Amine, gelatin, methylcellulose, carboxymethyl cellulose and its salt, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl Cellulose, maltodextrin and polymethacrylates.Such water-soluble polymer (no matter PVOH or other) can from it is a variety of come Source is commercially available.Any aforementioned water-soluble polymer is typically adapted to be used as film forming polymer.Water particularly suitable for capsule shells Soluble polymer include heat or melting it is machinable those, such as polyvinyl alcohol, polyethyleneimine, polyvinylpyrrolidone, Polyalkylene oxide, polyacrylamide, cellulose ether, cellulose esters, cellulose amides, polyvinyl acetate, polyamide, gelatin, first Base cellulose, carboxymethyl cellulose and its salt, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, wheat Bud dextrin, their copolymer, their blend and their combination.More specifically, for example, when non-thermal or non-melt processing When technology is for capsule shells formation (for example, using sintering process, mechanical processing technique or other forming technologies described below), Any one of aforementioned water-soluble polymer can be used in capsule shell material.In general, before water-soluble polymer composition may include State the copolymer and/or blend of resin.

For example, in the range of water-soluble polymer can be with about 30wt.% or 50wt.% to about 90wt.% or 95wt.% Amount be contained in polymer composition.For example, water-soluble polymer and all plasticizer, expanding material and secondary additive is total The weight ratio of amount can be about 0.5 to about 18, about 0.5 to about 15, about 0.5 to about 9, about 0.5 to about 5, about 1 to 3 or about 1 to 2 In range.

The spy of water-soluble polymer for polymer composition as described herein (including but not limited to PVOH polymer) Sign can be in about 3.0cP to about 27.0cP, about 4.0cP to about 23.0cP, about 4.0cP to about 15cP or about 6.0cP to about Viscosity in the range of 10.0cP.The viscosity of polymer is by using such as British Standard EN ISO15023-2:2006Annex E Brookfield LV type viscosity meter described in Brookfield test method with UL adapter is freshly prepared molten Liquid measures.Provide that viscosity of the 4% aqueous polyethylene alcoholic solution at 20 DEG C is international practice.Unless otherwise stated, this The polymeric viscosity in terms of cP that text is pointed out is interpreted as referring to viscosity of the 4% aqueous water-soluble polymer solution at 20 DEG C.

It is well known in the art, the viscosity of water-soluble polymer (PVOH or other) and the weight average point of same polymer Son amountCorrelation, and viscosity is typically used asIndex (proxy).Therefore, the weight averaged molecular of water-soluble polymer Amount can be in the range of about 30,000 to about 175,000 or about 30,000 to about 100,000 or about 55,000 to about 80,000.

Water-soluble polymer composition may include the other adjuvants and processing aid to be suitble to the amount of its desired use, example Such as, but not limited to, plasticizer, plasticizer expanding material, surfactant, lubricant, release agent, filler, incremental agent, crosslinking agent, anti- (such as layered silicate salt form nanoclay is (for example, sodium Ji Mengtuo for agglomeration agent, antioxidant, antitack agent, defoaming agent, nano particle Stone)), bleaching agent (for example, sodium pyrosulfite, sodium hydrogensulfite or other) and other functional components.It preferably includes to be plasticized The embodiment of agent.The amount of such reagent either individually or collectively may be up to about to body 50wt.%, 20wt%, 15wt%, 10wt%, 5wt.%, 4wt% and/or at least 0.01wt.%, 0.1wt%, 1wt% or 5wt%.

Plasticizer may include but be not limited to hydroxylating plasticizer, such as glycerol, diglycerol, ethylene glycol, diethylene glycol, three second Glycol, tetraethylene glycol, propylene glycol, the up to polyethylene glycol of 400MW, neopentyl glycol, trimethylolpropane, polyether polyol, 2- Methyl-1,3-propanediol, lactic acid, ethanol amine and their mixture.No matter the combination for single plasticizer or plasticizer, Such plasticizer (no matter for example, liquid form or other forms) at room temperature can be with about 10phr or 25phr to about Amount in the range of 30phr or 50phr, about 30phr to about 45phr or about 35phr to about 40phr is included in water-soluble polymeric In compositions.Water-soluble polymer composition optionally or additionally includes sugar alcohol plasticizer, for example including isomaltose, malt Sugar alcohol, D-sorbite, xylitol, antierythrite, ribitol (adonitol), dulcitol, pentaerythrite, mannitol and they Combination.No matter the combination for single sugar alcohol plasticizer or sugar alcohol plasticizer, sugar alcohol plasticizer can be with about 5phr to about Amount in the range of 35phr, about 5phr to about 25phr, about 10phr to about 20phr or about 10phr to about 15phr is included in poly- In polymer composition.The total amount of plasticizer can in about 5wt.% or 10wt.% to about 30wt.% or 40wt.% or about In the range of 15wt.% to about 35wt.% or about 20wt.% to about 30wt.%, for example, about 25wt.%.

Suitable surfactant may include nonionic, cation, anion and amphoteric ion classification.Suitable surface is living Property agent includes but is not limited to polyoxyethylated polyoxypropylene diols, alcohol ethoxylate, alkylphenol ethoxylate, tertiary acetylene series Two pure and mild alkanolamides (nonionic surfactant), polyoxyethylenated amine, quaternary ammonium salt and quaternized polyoxyethylenated amine (sun from Sub- surfactant) and amine oxide, N- alkyl betaine and sulfobetaines (zwitterionic surfactant).It is other suitable Surfactant include the Lactated aliphatic ester of dioctyl sodium sulphosuccinate, glycerol and propylene glycol, fatty acid lactoyl ester, Sodium alkyl sulfate, polysorbate20, polysorbate60, polysorbate65, polysorbate80, lecithin, glycerol and The acetylated fatty acid esters of propylene glycol and the acetylation ester and their combination of fatty acid.In various embodiments, water-soluble The amount of surfactant is in about 0.1wt% to 2.5wt%, optionally about 1.0wt% is to 2.0wt%'s in property polymer composition In range.

Suitable lubricants/release agents may include but be not limited to, fatty acid and its salt, fatty alcohol, fatty ester, fatty amine, Fatty amine acetates and fatty acid amide.Preferred lubricants/release agents are fatty acid, fatty acid salt and fatty amine acetates.? In a kind of embodiment, in water-soluble polymer composition the amount of lubricants/release agents about 0.02wt% to about 1.5wt%, Optionally in the range of about 0.1wt% to about 1wt%.

Suitable filler/incremental agent/anticaking agent/antitack agent includes but is not limited to, starch, modified starch, crosslinking it is poly- Vinylpyrrolidone, the cellulose of crosslinking, microcrystalline cellulose, silica, metal oxide, calcium carbonate, talcum and mica.It is excellent The material of choosing is starch, modified starch and silica.In a kind of embodiment, filler in water-soluble polymer composition/ Incremental agent/anticaking agent/antitack agent amount is in about 0.1wt% to about 25wt% or about 1wt% to about 10wt% or about In the range of 2wt.% to about 8wt.% or about 3wt.% to about 5wt.%.In the case where starch is not present, suitably fill out Material/incremental agent/anticaking agent/antitack agent preferred scope be about 0.1wt% or 1wt% to about 4wt% or 6wt% or about 1wt.% to about 4wt.% or about 1wt.% to about 2.5wt.%.

Water-soluble polymer composition can further have at least 4wt.%, such as in the range of about 4 to about 10wt.% Residual moisture content, such as by karr Fischer (Karl Fischer) titration measure.

The other feature of water-soluble polymer composition (such as film) (including including those of capsule shells) can be in U.S.'s public affairs It is found in cloth No. 2011/0189413 and U. S. application the 13/740th, 053, both is incorporated herein by reference in their entirety.

Forming and sealing

Water-soluble polymer composition can be formed into capsule shells element according to various techniques as known in the art.Example Such as, thermally processable water-soluble polymer can be selected and by melt processing (for example, injection molding) or hot forming skill Art is (described below) to be formed.In general injection molding process, the water-soluble polymer composition of capsule shells element will be used for (e.g., including any additional additive of water-soluble polymer and plasticizer etc.) it is fed in heating bucket, mixing, and press Enter in die cavity, it cools down and is hardened to the intended shape limited by mold (for example, each shell member as shown in the drawings here Part 210,220 and 230).The suitable melting of injection molding process and collector temperature can be in about 200 DEG C to about 220 DEG C of ranges It is interior (for example, for the PVOH polymer of suitable melt-processable；The temperature of other water-soluble polymers can be than respective The fusing point of polymer is about 10 DEG C to about 40 DEG C high).Bucket tip temperature can in the range of about 250 DEG C to about 300 DEG C (for example, than The fusing point of respective polymer is about 50 DEG C to about 150 DEG C high).The feeding part of bucket is set suitably to keep pleasantly cool (for example, about 40 DEG C), And the representative temperature of injection mold is about 60 DEG C to about 80 DEG C.Other useful hot-working process include compression forming；Casting The hot forming of sheet material, fused deposition (for example, 3D prints), the non-melt technique (example of spraying particles and fusion and, for example, sintering Such as, for example, by lower than crystallization or semi-crystalline polymer melting temperature at a temperature of, to powdered polymer materials carry out heat The coalescence of (and general pressure) induction is without liquefaction, to form solid or porous polymer shape).Suitably it is used for capsule Hull shape at non-thermal technologies example include solvent cast (for example, using water as solvent) and coating processes (such as spraying) and Mechanical processing technique (for example, capsule shells component is machined from the agglomerate of solid water soluble polymer).

Can also be according to various techniques as known in the art, such as by using heat in heat forming technology, make water solubility Polymer composition is configured to film (for example, to form the pouch for other than other ingredients also including sustained release capsule).It can Apply heat using any suitable method.For example, before film is fed on surface or once on the surface, which can pass through It passes through below heating element or is directly heated by hot-air.It optionally, can be for example by heating surface or by hot object Body is applied to indirect heating on film.Infrared light heating film can be used.Film can be heated to about 50 DEG C to about 150 DEG C, about 50 DEG C Temperature in the range of about 120 DEG C, about 60 DEG C to about 130 DEG C, about 70 DEG C to about 120 DEG C or about 60 DEG C to about 90 DEG C.It is optional Ground, can be by any suitable method wetting film, such as before being fed on surface or once on the surface, passes through spray It spills in wetting agent (including water, the solution of film composition, the plasticizer of film composition or any combination above-mentioned) to film directly Wetting, or soaked indirectly by wetting surface or by the way that wet object to be applied on film.

Once film has been heated and/or has soaked, it can be introduced in mold appropriate it is preferable to use vacuum.With suitable Composition (for example, according to the sustained release capsule of the disclosure, laundry composition in combination used etc.) fill mould plastic film It can be by being realized using any suitable method.For example, molding film can be filled by online filling technique.Then by appointing What suitable method is closed the unlimited parcel of filling using the second film, forms pouch.This can be simultaneously in horizontal position and even It is completed in continuous uniform motion.Closing, which can be achieved in that, is opening wide the second film (preferably water-solubility membrane) continuous feeding Above parcel and on it, then, usually between mold and thus preferably in the region between parcel, by the first film with Second film is sealed.

Using any suitable method of sealing parcel and/or its single compartment.The non-limiting example of such method Mean to include heat seal, solvent welding, solvent seal or wet sealing and their combination.In general, will only form the area of sealing Domain heat or solvent processing.Heat or solvent can apply by any method, be customarily applied on closed material, and usually only apply It is added on the region to form sealing.If preferably also applying heat using solvent or wet sealing or welding.Preferred wet sealing Or solvent seal/welding method includes passing through on the region that solvent selectivity is applied between mold or on closed material Such as sprayed or be printed on these regions, it then applies pressure on these regions, to form sealing.Such as it can be used Sealed roller and band as described above (heat is optionally also provided).

The water-soluble packet or pouch of formation can then be cut by cutter device.Any suitable side can be used in cutting Method is realized.Preferably cutting also in a continuous manner, and it is preferable to use at the uniform velocity, and is preferably in a horizontal position simultaneously.It cuts Cutting device may be, for example, sharp objects or hot object, thus in the case where hot object, in addition to slice other than or replacing in slice For in mode, hot object ` burns ` and wears film/seal area.The different compartments of multi-compartment pouches can be manufactured in together with pattern side by side, The pouch combined obtained in it can be separated by cutting or not separated.It optionally, can separately made compartment.It should be understood that It is that, by using feed station appropriate, can manufacture and be incorporated to many different or distinctive compositions and/or difference or distinctive liquid The multi-compartment pouches of body, gel or paste composition, such as wherein at least one compartment include the sustained release according to the disclosure Capsule

Water sensitivity composition

As described above, the capsule of the disclosure is for packaging (for example, directly contacting) water sensitivity composition (for example, alkaline material Material, cleaning combination) it is particularly advantageous, especially when being contacted with liquid water and/or vapor (no matter for example, room temperature/environment temperature Or high temperature) when produce those of gas (for example, oxygen).For example, inorganic bleaching agents can be generated when being exposed to water (liquid or gas) Hydrogen peroxide gas transfers to can be biodegradable into water and oxygen.Using this feature of the disclosure with keep comprising it is incompatible at Divide the composition of (for example, water sensitivity inorganic bleaching agents that are independent or combining with bleach-activating and/or bleaching catalyst and enzyme) It is physically separated from one another or is isolated.It is believed that such isolation can expand the service life of such components and/or reduce physical instability.

By the capsule prepared according to the water-soluble polymer of the disclosure, when the 1:1 mixture with sodium carbonate and SODIUM PERCARBONATE It is immersed in when contact in the water for the temperature for being heated to 40 DEG C, after subsequent capsule is completely dissolved, such as passes through bleach-compatible side Method A (hereafter) is measured, advantageously sustained release be contained therein water sensitivity composition (such as sodium carbonate or SODIUM PERCARBONATE drift White dose) at least 3 minutes, 5 minutes or 8 minutes, or as measured by bleach-compatible method B (hereafter), sustained release At least 9 minutes, 12 minutes or 15 minutes.

The suitable inorganic bleaching agents being used together with sustained release capsule include carbonate, borate, phosphate, sulfuric acid Salt and silicate and perhydrate (perhydrate) salt (such as perborate, percarbonate, perphosphate, over cure Hydrochlorate and persilicate).Inorganic bleaching agents are usually alkali metal salt (for example, lithium salts, sodium salt and/or sylvite).Inorganic bleaching agents Given salt suitably including its corresponding perhydrate salt (for example, sodium carbonate and SODIUM PERCARBONATE) combination, such as two The weight ratio of kind of component be about 1:1 (for example, given salt: the ratio of perhydrate salt be about 10:1 or 5:1 to about 1:5 or 1:10).May include in crystalline solid and without Additional Protection inorganic bleaching agents (for example, in powder type and without physical protection, such as Coating on solid particle or around the agglomeration agglomerate of solid).Optionally, inorganic bleaching agents can be coated or with other sides Formula encapsulation, such as with polyethylene glycol (for example, PEG-6000) or the protective coating of other coating substances as known in the art. Bleach-activating and/or bleaching catalyst (described below) may be included in the sustained release capsule with inorganic bleaching agents. Alternatively or additionally, bleach-activating and/or bleaching catalyst (when using) can be stored and/or from inorganic bleaching agents (examples Such as, when in the water-soluble pouch compartment separated with the capsule comprising inorganic bleaching agents) individually delivering.

It can be by the way that capsule to be stored to a period of time in the air environment of control to check their responses to it, to survey Their adaptation water of capsule of the examination comprising water sensitivity composition are exposed and no pressure gathers or the ability of capsule deformation.For example, working as At 80% relative humidity and 38 DEG C with the air environment of control (its reflect accelerated ageing environment be characterized in extend during capsule Shelf life) contact when, a kind of water sensitivity composition can produce gas.In a kind of embodiment, in 80% relative humidity and 38 DEG C Under store 4 weeks in the air environment of control the test phase after, capsule shells be substantially inflexible during the test phase (for example, During the test phase and/or at the end of there is no the flatulence that apparent or observation obtains), but the water sensitivity composition during the test phase Produce gas.This feature not deformed can for relative to corresponding initially capsule shells volume or enlarged-diameter 20%, 10%, 5%, 2%, the volume or diameter of 1% or below final inside capsule shells or outside.

At gas composition

As described above, the capsule of the disclosure is for packaging (for example, directly contacting) at gas composition, such as gas-generating agent composition Or air exhaust combination object (for example, essence combination) is particularly advantageous, especially discharge is in the gas of its native state (for example, combination Those of the volatile component of object, such as essence gas).Gas-generating agent composition includes into gas composition, is formed and discharges gas As gas-generating agent composition and another substance (such as water) (for example, when gas-generating agent composition is above-mentioned water sensitivity composition) or non-aqueous Substance (for example, including another composition in capsule, the component of capsule shells, the surrounding material in capsule) it is anti- Answer product.In contrast, air exhaust combination object includes into gas composition, such as in the case where liquid water and steam is not present, Its discharge gas and not necessarily with another substance reaction (for example, be not necessarily to and water or another environmental recovery bonds in internal capsule volume It learns substance reaction or has reaction to it in other ways).For example, in the case where essence combination, due to it is one or more its The natural volatility of liquid or solid volatility or perfume ingredient, such as essential oil, essential oil, aromatic compound etc. is (for example, normal The vapour pressure that can not ignore under the ambient storage conditions (for example, about 25 DEG C or 38 DEG C) seen), air exhaust combination object (such as volatility group Close object or essence combination) volatile component or essence gas can be discharged.Made us using this feature of the disclosure with providing Pleasant smell and/or with shelter from capsule, it includes pouch and/or its storage container other contents or component Unhappy people smell.

It is suitable as a variety of essence combinations of air exhaust combination object as is generally known in the art, such as in U.S. Patent No. 5,137, Disclosed in No. 646.For example, essence combination may include the solid matrix for loading essence, such as wherein by essence combination It is applied in solid delivery medium, is adsorbed onto, being adsorbed onto and wherein and/or be in other ways incorporated in.Other In embodiment, essence combination may include the liquid for loading essence, such as oil.In some cases, essence combination is row Gas composition, in its native state so that its perfume ingredient is fully exposed to external environment, to allow gas perfume ingredient (for example, typical or longest storage time) is discharged in the entire service life of essence combination.For example, essence combines Object can be loaded on porous carrier (for example, natural or synthetic polymer material, mineral material), such as load the ring of essence Dextrin, the zeolite for loading essence etc..In other cases, it is possible to provide essence is its perfume ingredient not being discharged in its native state Form；On the contrary, perfume ingredient sealed or store in other ways in the subsequent time (for example, it is from the disclosure Time after capsule sustained release) release.For example, the perfume ingredient of essence combination can be coated or encapsulate so that essence group It closes object and its perfume ingredient is not discharged substantially during storage (for example, essence coating or encapsulating material prevent or are greatly decreased gas Diffusion of the body perfume ingredient during storage).The example of such essence combination includes with other protectiveness shell (for example, outer Portion's polymer coating) it encapsulates internal perfume ingredient and loads the solid matrix (for example, as described above) of essence to be restricted or prevented The microcapsules of perfume ingredient release.The essence combination of such coating or encapsulation is expectable in laundry or other cleaning frequencies It is interior from capsule sustained release (for example, releasable perfume ingredient or essence combination can be attached to the article just cleaned at this time).

Cleaning combination

Including cleaning or detergent composition (such as clothing, laundry additive, fabric intensifier and/or dishwashing group Close object) capsule or pouch in, composition may include one of following non-limiting ingredient lists or a variety of: fabric nursing by Beneficial agent；Detergency enzymes；Deposition aid；Rheology modifier；Help net agent；Inorganic bleaching agents (described above), organic bleaches；Drift White dose of precursor；Bleach boosters (or activator)；Bleaching catalyst；Essence and/or essence micro-capsule (see, for example, US 5,137, 646)；Load the zeolite of essence；The temper (accord) of starch encapsulation；Polyglycerol ester；Brightening agent；Pearling agent；Enzyme liptinite System；Cleanser (complexing agent and their mixture of fixative, anionic surfactant including anionic dye)；Optics Brightening agent or fluorescer；Polymer (including but not limited to soil release polymer and/or soil suspension polymer)；Dispersing agent； Defoaming agent；Non-aqueous solvent；Fatty acid；Foam inhibitor, such as silicone foam inhibitor (U.S.'s announcement the 2003/0060390A1st, the Page 65~77)；Cationic starch (US 2004/0204337A1 and US 2007/0219111A1)；Scum Dispersants (US 2003/0126282A1, page 89~90)；Dyestuff；Colorant；Opacifiers；Antioxidant；Hydrotrote, such as toluenesulfonic acid Salt, cumene sulfonate and naphthalene sulfonate；Color tablets (color speckle)；Colour bead, sphere or extrudate；Clay is soft Agent.Any one or more of these ingredients are further described in European Patent Application No. 09161692.0, U.S.'s public affairs In cloth No. 2003/0139312A1 and U.S. Patent Application No. 61/229981.Additionally or alternatively, composition may include table Face activating agent and/or dicyandiamide solution, are respectively described below.

Detergent composition may include such as by weight about 1% to 80% surfactant.The decontamination table utilized Face activating agent can for anion, nonionic, amphoteric ion, amphoteric or cationic or may include these types compatibility Mixture.In a kind of embodiment, surfactant be selected from by anion, nonionic and cationic surfactant and it Mixture composition group in.Composition can be substantially free of beet alkali surface activator.Detergent surface used herein The example of activating agent is described in United States Patent (USP) 3,664,961；3,919,678；In 4,222,905 and 4,239,659.Another kind of In embodiment, surfactant is selected from and is made of anionic surfactant, nonionic surfactant and their combination Group in.

Useful anionic surfactant itself can have a variety of different types.For example, the water solubility of higher fatty acids Salt, i.e. " soap " are the anionic surfactant in composition herein.This includes alkali metal soap, such as comprising about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms higher fatty acids sodium, potassium, ammonium and alkylammonium salt.Soap can pass through rouge Fat and oily Directly saponification are prepared by the neutralization of free fatty acid.The particularly useful rouge for being derived from coconut oil and butter The sodium and sylvite of the mixture of fat acid, i.e. sodium or potassium butter and coconut soap.

It is suitble in other non-soap anionic surfactant used herein include water soluble salt, preferably in its molecule knot There is the alkali gold of organic sulfuric acid reaction product of the alkyl comprising about 10 to about 20 carbon atoms and sulfonic acid or sulfate group in structure Category and ammonium salt.(including the moieties of acyl group in term " alkyl ".) examples of the combination forming surfactants includes: a) alkane Base sodium sulphate, alkylsurfuric acid potassium and alkylsurfuric acid ammonium, especially by by higher alcohol (C₈-C₁₈) obtained by sulphation those, example Such as by reduction butter or coconut oil glyceride it is generated those；B) the poly- ethoxy of alkyl polyethoxylate sodium sulphate, alkyl Base potassium sulfate and alkyl polyethoxylate ammonium sulfate, especially wherein alkyl includes 10 to 22, preferably 12 to 18 carbon Atom, and wherein polyethoxy chain includes those of 1 to 15, preferably 1 to 6 ethoxylate part；And c) wherein with Straight chain or branched chain, sodium alkyl benzene sulfonate and alkyl benzene sulphonate potassium of the alkyl comprising about 9 to about 15 carbon atoms, for example, Those types described in United States Patent (USP) 2,220,099 and 2,477,383.Especially valuable is linear straight chain benzene sulphur Acid esters, wherein the average carbon atom number in alkyl is about 11 to 13, is abbreviated as C₁₁-C₁₃LAS。

Nonionic surfactant can be selected from formula R₁(OC₂H₄)_nIt is one or more in those of OH, wherein R₁For C₁₀-C₁₆ Alkyl or C₈-C₁₂Alkyl phenyl, and n is 3 to about 80.It is specifically contemplated that C₁₂-C₁₅Alcohol and about 5 moles to about 20 moles of epoxy second Alkane/mol of alcohol condensation product, such as C₁₂-C₁₃Alcohol and about 6.5 moles of ethylene oxide/mol of alcohol are condensed.

Dicyandiamide solution in the present composition can be the solvent of the mixture comprising individual water or organic solvent and water System.Organic solvent may include 1,2- propylene glycol, ethyl alcohol, glycerol, dipropylene glycol, methyl propanediol and their mixture.? Other lower alcohols, C can be used₁-C₄Alkanolamine (such as monoethanolamine and triethanolamine).Such as it is real in the anhydrous solid of the disclosure It applies in mode, dicyandiamide solution may not be present, but dicyandiamide solution is more generally with about 0.1% to about 98%, preferably at least about 1% to about 50%, horizontal in the range of more typically from about 5% to about 25% exists.

Organic bleaches may include organic peroxide acid (including diacyl and four acyl peroxides, especially diperoxy ten Two docosandioic acids, diperoxy tetracosandioic acid and diperoxy hexadecandioic acid (hexadecane diacid)).Organic peroxide acid can be dibenzoyl peroxidating Object.Diacyl peroxide, especially dibenzoyl peroxide can with have for example, about 0.1 micron to about 100 microns, The form of the particle of preferably from about 0.5 micron to about 30 microns, more preferably from about 1 micron to about 10 microns of weight mean diameter is deposited ?.In embodiments, at least about 25% to 100% or at least about 50% or at least about 75% or at least about 90% Grain is less than 10 microns, and optionally less than 6 microns.

Other organic bleaches include peroxy acid, and specific example is alkyl peroxy acids and aryl peroxy acids.Representative includes: (a) benzoyl hydroperoxide and its cyclosubstituted derivative, such as alkyl peroxy benzoic acid, there are also peroxide-α-naphthoicacid and list are excessively adjacent Phthalic acid magnesium；(b) aliphatic series or the aliphatic peroxy acids replaced, such as peroxide lauric acid, peroxystearic acid, ε-phenyl-diformyl imido Base peroxy caproic acid [phthaloyl imino peroxy caproic acid (PAP)], phthalamidic acid base peroxy caproic acid, N- nonenyl acyl Amido crosses adipic acid and N- nonenyl amide groups crosses succinate；(c) aliphatic series and araliphatic peracetic acid, such as 1,12- Diperoxy carboxylic acid, 1,9- diperoxyazelaic acid, diperoxy decanedioic acid, diperoxy brassylic acid, diperoxy phthalic acid, the 2- last of the ten Heavenly stems Base diperoxy butyl- 1,4- diacid, N, N- terephthaloyl groups two (6- aminopercaproic acid).

Bleach-activating may include the organic peracid for enhancing blanching effect in cleaning process under 60 DEG C and lower temperature Precursor.Be suitble to obtain in the case where bleach-activating used herein is included in peroxide hydrolysising condition to have preferably 1 to 10 carbon atom, The aliphatic peroxycarboxylic acid of especially 2 to 4 carbon atoms, and/or the compound of benzoyl hydroperoxide optionally replaced.Suitable substance Carry the O- acyl group and/or N- acyl group of specified amount of carbon atom, and/or the benzoyl optionally replaced.It is preferred that poly- be acylated Asia Alkyl diamine, especially tetra acetyl ethylene diamine (TAED), acylated pyrrolotriazine derivatives, especially 1,5- diacetyl -2,4- bis- Oxo hexahydro -1,3,5-triazines (DADHT), acylated glycolurils, especially tetra-acetylated glycoluril (TAGU) are N- imide, outstanding It is N- nonanoylsuccinimide (NOSI), acylated phenol sulphonic acid ester, especially positive pelargonyl group or different nonyl acyl oxygroup benzene sulphur Acid esters (positive NOBS or different NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydroxy-alcohol, especially triacetic acid glycerol Ester, ethylene acetate and 2,5- diacetoxy -2,5-dihydrofuran and CitroflexA-2 (TEAC). Bleach-activating the combination of its corresponding organic or inorganic bleaching agent and/or can be stored separately and/or be delivered (for example, having Have in the capsule of inorganic bleaching agents or the capsule that is separated with inorganic bleaching agents in, such as in water-solubility membrane parcel).

It include manganese 7-triazacyclononane and related complexes with the bleaching catalyst in detergent composition in this article (US-4,246,612,US-A-5,227,084)；The bis- pyridyl group amine of Co, Cu, Mn and Fe and related complexes (US-5,114, 611)；With five amine cobalt acetates (III) and related complexes (US-4,810,410).It is suitble to bleaching catalyst used herein Another description can be seen in incorporated herein by reference U.S. Patent No. 6,599,871.Bleaching catalyst can Its corresponding bleach-activating and organic or inorganic bleaching agent combine and/or are stored separately and/or deliver (for example, having Have in the capsule of inorganic bleaching agents or the capsule that is separated with inorganic bleaching agents in, such as in water-solubility membrane parcel).

The net agent that helps suitable for detergent composition as described herein includes that water solubility helps net agent, including citrate, Carbonate, silicate and polyphosphate, such as sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixing Sodium tripolyphosphate and sylvite.

Enzyme suitable for detergent composition as described herein includes bacterium and fungal cellulase, including CAREZYME and CELLUZYME (Novo Nordisk A/S)；Peroxidase；Lipase, including AMANO-P (Amano Pharmaceutical Co.), M1LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASE and LIPOLASE ULTRA(Novo)；Cutinase；Protease, including ESPERASE, ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades)；α and beta amylase, including PURAFECT OX AM (Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL and NATALASE (Novo)；Pectase；With mixing for they Close object.Based on the weight of cleaning combination, in the range of enzyme herein can be with normally about 0.0001% to about 2% pure enzyme Level is added as spherolite (prill), particle or total particle (cogranulates).

Being suitble to the foam inhibitor used in detergent composition as described herein includes the non-ionic surface with low cloud point Activating agent." cloud point " is the known property of nonionic surfactant as used herein, is surfactant with temperature Degree increases and becomes less soluble as a result, the temperature that the appearance of the second phase can be observed is referred to as " cloud point ".As made herein With " low cloud point " nonionic surfactant is defined as lower than 30 DEG C, preferably less than about 20 DEG C even more preferably less than The nonionic surfactant system ingredient of about 10 DEG C, more preferably less than about 7.5 DEG C of cloud point.Low cloud point non-ionic surface active Agent may include Nonionic alkoxylated surfactant, especially be derived from the ethoxylate and polyoxypropylene/polyoxy of primary alconol Ethylene/polyoxypropylene (PO/EO/PO) reversed block polymer.Moreover, such low cloud point non-ionic surfactants may include, Such as poly- (the alkoxy of ethoxylated-propoxylated alcohol (for example, BASF POLY-TERGENT SLF18) and ethyoxyl sealing end Change) alcohol (for example, the nonionic surfactant of BASF POLY-TERGENT SLF18B series, as example in US-A-5,576, Described in 281).

It include being discharged with antiredeposition, soil for other suitable components in detergent composition as described herein Or the cleaning cleaning polyalcohol of other decontamination properties.It include polymer containing acrylic acid, example in antiredeposition polymer used herein Such as SOKALAN PA30, PA20, PA15, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid, such as SOKALAN CP5 and acrylic acid/methacrylic acid copolymer.? Soil release polymer used herein includes alkyl and hydroxy alkyl cellulose (US-A-4,000,093), polyoxyethylene, gathers Oxypropylene and their copolymer and terephthalate based on ethylene glycol, propylene glycol and their mixture it is non-from Son and anionic polymer.

Heavy metal chelant and crystal growth inhibitor can be also suitably used in detergent, such as in its salt and free acid form Diethylenetriamine five (methene phosphonate ester), ethylenediamine tetraacetic (methene phosphonate ester), hexamethylene diamine four (methene phosphonate ester), sub- Ethyl bisphosphonates, hydroxy-ethylene -1,1- bisphosphonates, nitrilotriacetate, second diaminetetracetic acid esters, ethylenediamine - N, N'- disuccinic acid ester.

Suitable for the also corrosion inhibitor of detergent composition as described herein, such as organic silver coating agent is (especially Paraffin, for example, by Germany Wintershall, Salzbergen sale WINOG 70), nitrogenous corrosion inhibitor compound (such as benzotriazole and benzimidazole-are referring to GB-A-1137741) and Mn (II) compound, the especially Mn of organic ligand (II) salt.

In suitable component include enzyme stabilizers for other conjunctions in this paper detergent composition, for example, calcium ion, boric acid and Propylene glycol.

Suitable rinsing additive is known in the art.Business rinse aid for dishwashing is usually low foam rouge Fat alcohol polyethylene/polypropylene glycol ether, solubilizer (such as isopropyl sulfonic acid ester), organic acid (such as citric acid) and solvent (such as Ethyl alcohol) mixture.The function of such rinse aid is the interfacial tension of influence water, by this method can be from thin cohesion The rinsed surfaces of form membrane drain, to not leave water droplet, striped or film after subsequent drying process.European patent 0 197 434 B1 describe the rinse aid comprising compound ether as surfactant.Also consider the drift of fabric softener etc. It washes additive and it is suitble to be encapsulated in the film according to content disclosed herein.

The aspect of present disclosure specifically considered describes in the paragraph of lower column number herein.

1, a kind of sustained release capsule for delivering compositions, the capsule includes: (a) simultaneously comprising water-soluble polymer The capsule shells of the inside capsule volume of sealing are limited, wherein the capsule shells have in the range of about 100 μm to about 5000 μm Wall thickness；(b) composition for sustained release being contained in the inside capsule volume of the sealing.

2, the capsule as described in paragraph 1, wherein the composition includes cleaning combination.

3, the capsule as described in either segment in aforementioned paragraphs, in which: (i) described capsule shells include two or more together Cooperate to limit the capsule shells element of the inside capsule volume of the capsule shells and the sealing jointly；And (ii) each capsule Shell element includes the water-soluble polymer.

4, the capsule as described in either segment in aforementioned paragraphs, wherein the composition be not when in liquid water and steam At least one contact when can produce the water sensitivity composition of gas.

5, the capsule as described in either segment in aforementioned paragraphs is worked as and liquid water and water wherein the internal sizes capsule volume is free of At least one of steam can produce the water sensitivity composition of gas when contacting.

6, a kind of capsule for delivering compositions, the capsule includes: (a) including water-soluble polymer and limits inside The capsule shells of capsule volume, wherein (i) capsule shells have the wall thickness in the range of about 100 μm to about 5000 μm, and (ii) The capsule shells include pin hole, and the pin hole is sized with shape so that (A) is allowed in the internal capsule volume and institute It states gaseous fluid between the environment outside capsule shells to communicate, and (B) is limited in the internal capsule volume and the external rings Liquid fluid communicates between border；And it (b) is contained in the composition in the internal capsule volume, wherein the internal sizes capsule holds Product is without the water sensitivity composition that can produce gas when contacting at least one of liquid water and steam.

7, the capsule as described in paragraph 6, wherein the pin hole has the diameter in the range of about 10 μm to about 1500 μm (D)。

8, the capsule as described in either segment in paragraph 6 or 7, wherein the pin hole has length (L) and diameter (D): corresponding L/D ratio in the range of about 0.01 to about 100.

9, the capsule as described in either segment in paragraph 6 to 8, in which: (i) described capsule shells include two or more together Cooperate to limit the capsule shells element of the capsule shells and the internal capsule volume jointly；(ii) each capsule shells element includes The water-soluble polymer；And (iii) at least one capsule shells element includes the pin hole.

10, the capsule as described in either segment in paragraph 6 to 9, wherein the composition includes air exhaust combination object.

11, the capsule as described in paragraph 10, wherein the air exhaust combination object includes volatile compositions, the volatility group Close the volatile component that the volatile compositions can be discharged in object in gaseous form.

12, the capsule as described in paragraph 10, wherein the air exhaust combination object includes the essence group that can issue essence gas Close object.

13, the capsule as described in paragraph 12, wherein the essence combination includes the solid matrix for loading essence.

14, the capsule as described in either segment in paragraph 6 to 9, wherein it is that liquid water and water steam that the composition, which is included in not, The gas-generating agent composition of gas can be produced in the presence of the reactive component of gas.

15, the capsule as described in either segment in paragraph 6 to 14, wherein the capsule further comprises being contained in the inside Additional composition in capsule volume, and at least one of the composition and the additional composition are intended for delay and release It puts.

16, the capsule as described in either segment in aforementioned paragraphs, wherein the internal sizes capsule volume is in about 0.1ml to about In the range of 100ml.

17, the capsule as described in either segment in aforementioned paragraphs, wherein range of the wall thickness at about 250 μm to about 1500 μm It is interior.

18, the capsule as described in either segment in aforementioned paragraphs, wherein the capsule shells have substantially homogeneous wall thickness.

19, the capsule as described in paragraph 18, wherein the capsule shells wall has substantially being averaged across entire capsule shells About 50% interior local thickness of wall thickness.

20, the capsule as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer is hot formed.

21, the capsule as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer has about 4cP at 20 DEG C 4% solution viscosity in the range of to about 23cP.

22, the capsule as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer is selected from by polyvinyl alcohol, gathers Aziridine, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose esters, cellulose amides, gathers at polyvinylpyrrolidone Vinyl acetate, polyamide, gelatin, methylcellulose, carboxymethyl cellulose and its salt, dextrin, ethyl cellulose, ethoxy are fine Tie up the group of element, hydroxypropyl methyl cellulose, maltodextrin, their copolymer, their blend and their combination composition In.

23, the capsule as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer includes polyvinyl alcohol.

24, the capsule as described in paragraph 23, wherein the polyvinyl alcohol has the water in the range of about 75% to about 99% Xie Du.

25, the capsule as described in paragraph 23, wherein the polyvinyl alcohol includes substantially by vinyl alcohol monomer repetitive unit With the polyvinyl alcohol copolymer of vinyl acetate monomer repetitive unit composition.

26, the capsule as described in paragraph 23, wherein the polyvinyl alcohol includes to contain vinyl alcohol monomer repetitive unit, acetic acid The polyvinyl alcohol copolymer of vinyl acetate monomer repetitive unit and the monomeric repeating unit of at least one other type.

27, the capsule as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 5 minutes to 20 minutes complete.

28, the capsule as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 20 minutes to 50 minutes complete.

29, the capsule as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 50 minutes to 100 minutes complete.

30, the capsule as described in either segment in aforementioned paragraphs, wherein the composition be selected from by laundry detergent composition, In the group that fabric intensifier, organic bleaches, essence and their combination form.

31, the capsule as described in paragraph 30, wherein the capsule is at a temperature of in the range of about 20 DEG C to about 25 DEG C Visible residue is not left on clothing when washing together with clothing in unheated washing cycle 61 minutes.

32, the capsule as described in paragraph 30, wherein the capsule is when the temperature of (i) in the range of about 20 DEG C to about 25 DEG C Under wash 61 minutes together with clothing in unheated washing cycle, then (ii) is in the range of about 20 DEG C to about 25 DEG C At a temperature of when rinsing 36 minutes together with clothing, visible residue is not left on clothing.

33, a kind of capsule for delivering volatile composition, the capsule includes: (a) including polyvinyl alcohol and limits The water-soluble glue softgel shell of internal capsule volume, in which: (i) described capsule shells have in the range of about 250 μm to about 3000 μm Wall thickness, and (ii) described capsule shells include pin hole, and the pin hole is sized with shape to which (A) is allowed in the inside Gaseous fluid communicates between capsule volume and the external environment of the capsule shells, and (B) is limited in the internal capsule volume Liquid fluid communicates between the external environment；(b) volatile compositions being contained in the internal capsule volume, institute State the volatile component that the volatile compositions can be discharged in volatile compositions with gas procedure.

34, the capsule as described in paragraph 33, wherein the capsule shells have the base in the range of about 250 μm to about 1500 μm This uniform wall thickness.

35, the capsule as described in either segment in paragraph 33 to 34, wherein the capsule also includes: (c) is contained in described Additional composition in portion's capsule volume, wherein the additional composition is intended for from the capsule sustained release.

36, the capsule as described in paragraph 35, wherein the additional composition is selected from micro- by the perfume particles and essence that coat In the group of capsule composition.

37, the capsule as described in either segment in paragraph 33 to 36, wherein the volatile compositions include that work can be discharged For the perfume compositions of the fragrance gas of the volatile component.

38, the capsule as described in either segment in paragraph 33 to 36, wherein the volatile compositions include that work can be discharged For the essence combination of the essence gas of the volatile component.

39, the capsule as described in paragraph 38, wherein the essence combination includes the solid matrix for loading essence.

40, the capsule as described in either segment in paragraph 33 to 39, wherein the internal sizes capsule volume be free of when and liquid water With the water sensitivity composition that can produce gas when the contact of at least one of vapor.

41, a kind of product, it includes: (a) comprising water-solubility membrane and limit (i) inner pouch volume and (ii) optionally needle The water-soluble pouch in hole, the pin hole are sized small to be allowed in the inner pouch volume and the water solubility with shape It is in fluid communication between environment outside bag；(b) be contained in the inner pouch volume according to either segment institute in aforementioned paragraphs The capsule stated, wherein the water-soluble pouch includes the pin hole (i) when the capsule also includes the pin hole, and (ii) the capsule shells pin hole existing for and the existing water-soluble pouch pin hole are in fluid communication；(c) it is contained in described Laundry detergent composition in portion's pouch volume.

42, the product as described in paragraph 41, in which: (i) described inner pouch volume include at least (A) first compartment and (B) with the second compartment of the first compartment physical separation；(ii) first compartment limits the existing pouch pin hole, and It and include the capsule；And (iii) described second compartment includes the laundry detergent composition.

43, the article as described in paragraph 41 or 42, wherein the water-solubility membrane includes water-soluble polymer, the water solubility Polymer can be identical or different with the water-soluble polymer of the capsule shells.

44, a kind of method for washing clothing, which comprises (a) forms Aqueous wash in washing container and be situated between Matter, the Aqueous wash medium is comprising (i) water, (ii) clothing, (iii) laundry detergent composition with (iv) according to aforementioned paragraphs Capsule described in middle either segment, wherein the composition includes cleaning combination；And it (b) is washed in the Aqueous wash medium Wash the clothing；Wherein until reaching selected delay washing cycle until adding the capsule to the water-based liquid medium Time, the cleaning combination are just discharged from the capsule.

45, the method as described in paragraph 44, wherein by the capsule and the laundry detergent composition with such as paragraph 41 Form to product described in either segment in 43 is added to the washing container.

46, the method as described in paragraph 44 or 45, wherein the clothing is at the end of washing without due to the capsule shells The visible residue of dissolution and generation.

47, the method as described in either segment in paragraph 44 to 46 further comprises: (c) removes institute from the washing container State Aqueous wash medium, rather than the clothing and the capsule；(d) aqueous rinse medium is formed in the washing container, The aqueous rinse medium includes (i) water, (ii) clothing cleaned and (iii) described capsule；And (e) in the aqueous drift It washes in medium and rinses the clothing；Wherein the selected delay time washing cycle long enough so that the cleaning combination from The capsule is discharged into the aqueous rinse medium.

48, the method as described in either segment in paragraph 44 to 46 further comprises: (c) removes institute from the washing container State Aqueous wash medium, rather than clothing；(d) aqueous rinse medium is formed in the washing container, the aqueous rinse is situated between Matter includes the clothing that (i) water and (ii) were cleaned；And the clothing (e) is rinsed in the aqueous rinse medium；Wherein institute State that selected delay time washing cycle is short enough so that the cleaning combination is discharged into the Aqueous wash from the capsule In medium.

49, a kind of method for delayed release compositions into water-based liquid medium, which comprises (a) is provided The capsule according to either segment in aforementioned paragraphs, wherein the composition includes cleaning combination；(b) capsule is added To the water-based liquid medium comprising water；And dissolve the capsule shells (c) to discharge the cleaning combination to the aqueous solution In body medium, wherein reach selected delay time until the capsule is added to the water-based liquid medium, it is described Cleaning combination is just discharged into the water-based liquid medium from the capsule.

50, the method as described in paragraph 49, wherein the delay time is at least about 10 minutes.

51, the method as described in paragraph 49, wherein the delay time is at least about 15 minutes.

52, a kind of free-standing sustained release capsule, it includes: comprising water-soluble polymer and limit the inside capsule of sealing The capsule shells of volume, in which: (i) described capsule shells have the wall thickness in the range of about 100 μm to about 5000 μm, and (ii) institute Capsule shells are stated with substantially homogeneous wall thickness.

53, the capsule as described in paragraph 52, wherein the inside capsule volume of the sealing is in about 0.1ml to about 100ml's In range.

54, the capsule as described in either segment in paragraph 52 or 53, wherein model of the wall thickness at about 250 μm to about 1500 μm In enclosing.

55, the capsule as described in either segment in paragraph 52 to 54, wherein the capsule shells wall has substantially across entire Local thickness in the 50% of the average wall thickness of capsule shells.

56, the capsule as described in either segment in paragraph 52 to 55, in which: (i) described capsule shells include two or more Cooperate together to limit the capsule shells element of the capsule shells and the internal capsule volume jointly；And (ii) each capsule shells Element includes the water-soluble polymer.

57, a kind of method for being used to prepare the capsule for sustained release delivering compositions, which comprises (a) choosing Select the expectation composition for sustained release delivering；(b) expectation aqueous medium condition of the selection for sustained release delivering, it is described Aqueous medium condition includes temperature, composition and the stirring condition of the composition aqueous medium to be delivered to of institute's sustained release；(c) Select the expected delay time for the composition that be discharged into the aqueous medium；(d) wall thickness and water-soluble polymeric are selected Object, so as to have the selected wall thickness of the capsule shells, the water-soluble polymer of the selected capsule shells and the internal sizes The capsule of expectation composition in capsule volume formed according to either segment in aforementioned paragraphs, until when the capsule and with institute's phase The expected delay time hoping the aqueous medium contact of aqueous medium condition and reaching, just discharge the expectation composition；And (e) Being formed, there is the selected wall thickness of the capsule shells, the water-soluble polymer of the selected capsule shells and the internal capsule to hold The capsule according to either segment in aforementioned paragraphs of expectation composition in product.

1A. is a kind of for delivering the sustained release capsule of water sensitivity composition, and the capsule includes: (a) comprising water solubility Polymer and the capsule shells for limiting internal capsule volume, wherein (i) capsule shells have about 100 μm to about 5000 μm of range Interior wall thickness, and (ii) described capsule shells include pin hole, and the pin hole is sized described to which (A) is allowed in shape Gaseous fluid communicates between environment outside internal capsule volume and the capsule shells, and (B) is limited in the internal capsule Liquid fluid communicates between volume and external environment；And it (b) is contained in the water sensitivity composition in the internal capsule volume, The water sensitivity composition can produce gas when contacting at least one of liquid water and steam.

Capsule of the 2A. as described in paragraph 1A, wherein the internal sizes capsule volume is in the range of about 0.1ml to about 100ml.

Capsule of the 3A. as described in either segment in aforementioned paragraphs, wherein range of the wall thickness at about 250 μm to about 1500 μm It is interior.

Capsule of the 4A. as described in either segment in aforementioned paragraphs, wherein the pin hole has about 10 μm to about 1500 μm of model Enclose interior diameter (D).

Capsule of the 5A. as described in either segment in aforementioned paragraphs, wherein the pin hole has length (L) and diameter (D): corresponding L/D ratio in the range of about 0.01 to about 100.

Capsule of the 6A. as described in either segment in aforementioned paragraphs, wherein the capsule shells have substantially homogeneous wall thickness.

Capsule of the 7A. as described in paragraph 6A, wherein the capsule shells wall has substantially being averaged across entire capsule shells Local thickness in about the 50% of wall thickness.

Capsule of the 8A. as described in either segment in aforementioned paragraphs, in which: (i) described capsule shells include two or more one Cooperation is played to limit the capsule shells element of the capsule shells and the internal capsule volume jointly；(ii) each capsule shells element packet Containing the water-soluble polymer；And (iii) at least one capsule shells element includes the pin hole.

Capsule of the 9A. as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer is hot formed.

Capsule of the 10A. as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer has about at 20 DEG C 4% solution viscosity in the range of 4cP to about 23cP.

Capsule of the 11A. as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer be selected from by polyvinyl alcohol, Polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose esters, cellulose amides, Polyvinyl acetate, polyamide, gelatin, methylcellulose, carboxymethyl cellulose and its salt, dextrin, ethyl cellulose, ethoxy What cellulose, hydroxypropyl methyl cellulose, maltodextrin, their copolymer, their blend and their combination formed In group.

Capsule of the 12A. as described in either segment in aforementioned paragraphs, wherein the water-soluble polymer includes polyvinyl alcohol.

Capsule of the 13A. as described in paragraph 12A, wherein the polyvinyl alcohol has in the range of about 75% to about 99% Degree of hydrolysis.

Capsule of the 14A. as described in paragraph 12A, wherein the polyvinyl alcohol includes substantially to repeat list by vinyl alcohol monomer The polyvinyl alcohol copolymer of member and vinyl acetate monomer repetitive unit composition.

Capsule of the 15A. as described in paragraph 12A, wherein the polyvinyl alcohol includes to contain vinyl alcohol monomer repetitive unit, second The polyvinyl alcohol copolymer of vinyl acetate monomeric repeating unit and the monomeric repeating unit of at least one other type.

Capsule of the 16A. as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method A, It is kept when being formed by capsule shells in the water for being immersed in the temperature for being heated to about 40 DEG C at least about 8 minutes complete.

Capsule of the 17A. as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method A, It is kept when being formed by capsule shells in the water for being immersed in the temperature for being heated to about 40 DEG C at least about 12 minutes complete.

Capsule of the 18A. as described in either segment in aforementioned paragraphs, wherein as measured by bleach-compatible method B, It is kept when being formed by capsule shells in the water for being immersed in the temperature for being heated to about 40 DEG C at least about 15 minutes complete.

Capsule of the 19A. as described in either segment in aforementioned paragraphs, wherein the capsule works as the range at about 20 DEG C to about 25 DEG C Visible remnants are not left on clothing when washing together with clothing in unheated washing cycle 61 minutes at a temperature of interior Object.

Capsule of the 20A. as described in either segment in aforementioned paragraphs, wherein the capsule is when (i) is at about 20 DEG C to about 25 DEG C At a temperature in the range of washed together with clothing in unheated washing cycle 61 minutes, then (ii) is at about 20 DEG C to about 25 When rinsing together with clothing at a temperature of in the range of DEG C 36 minutes, visible residue is not left on clothing.

Capsule of the 21A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition is steamed when with liquid water and water At least one of gas can generate oxygen when contacting.

Capsule of the 22A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition is worked as and 80% relative humidity Gas is produced when the air environment contact of the control at 38 DEG C.

Capsule of the 23A. as described in either segment in aforementioned paragraphs, in which: (i) described water sensitivity composition is when opposite with 80% The air environment of control at humidity and 38 DEG C produces gas when contacting 4 weeks test phases；And (ii) described capsule shells are in the test phase Period is substantially inflexible.

Capsule of the 24A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition is alkaline.

Capsule of the 25A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition includes selected from by carbonic acid Salt, borate, phosphate, sulfate, silicate, percarbonate, perborate, perphosphate, persulfate, persilicate and Inorganic bleaching agents in the group of their combination composition.

Capsule of the 26A. as described in paragraph 25A, wherein the inorganic bleaching agents composition includes SODIUM PERCARBONATE and sodium carbonate.

Capsule of the 27A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition include inorganic bleaching agents, And at least one of bleach-activating and bleaching catalyst.

Capsule of the 28A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition is in powder type.

Capsule of the 29A. as described in either segment in aforementioned paragraphs, wherein the water sensitivity composition is uncoated.

30A. is a kind of for delivering the sustained release capsule of water sensitivity composition, and the capsule includes: (a) including polyethylene Alcohol and the water-soluble glue softgel shell for limiting internal capsule volume, in which: (i) capsule shells are with about 250 μm to about 3000 μm Wall thickness in range, and (ii) described capsule shells include pin hole, the pin hole is sized with shape to which (A) is allowed in institute It states gaseous fluid between the environment outside internal capsule volume and the capsule shells to communicate, and (B) is limited in the internal sizes Liquid fluid communicates between capsule volume and external environment；(b) the water sensitivity composition being contained in the internal capsule volume, The water sensitivity composition (i) can generate hydrogen peroxide gas when contacting at least one of liquid water and steam, And (ii) includes selected from by carbonate, borate, phosphate, sulfate, silicate, percarbonate, perborate, peroxophosphoric acid The inorganic bleaching agents in group that salt, persulfate, persilicate and their combination form.Sustained release as described in paragraph 30 Capsule can be improved or be extended as described in either segment in aforementioned paragraphs.

Capsule of the 31A. as described in paragraph 30A, wherein the capsule shells have in the range of about 250 μm to about 1500 μm Substantially homogeneous wall thickness.

Capsule of the 32A. as described in paragraph 30A or 31A, wherein the water sensitivity composition further includes bleach-activating At least one of with bleaching catalyst.

A kind of product of 33A., it includes: (a) comprising water-solubility membrane and limit (i) inner pouch volume and (ii) pin hole Water-soluble pouch, the pin hole are sized with shape to be allowed in outside the inner pouch volume and the water-soluble pouch It is in fluid communication between the environment in portion；(b) be contained in the inner pouch volume according to either segment in aforementioned paragraphs Capsule, wherein the capsule shells pin hole and the water-soluble pouch pin hole are in fluid communication；(c) inner pouch is contained in hold Laundry detergent composition in product.

Product of the 34A. as described in paragraph 33A, in which: (i) described inner pouch volume include at least (A) first compartment and (B) with the second compartment of the first compartment physical separation；(ii) first compartment limits the pouch pin hole, and includes The capsule；And (iii) described second compartment includes the laundry detergent composition.

Product of the 35A. as described in paragraph 33A or 34A, wherein the water-solubility membrane includes water-soluble polymer, the water Soluble polymer can be identical or different with the water-soluble polymer of the capsule shells.

A kind of method for washing clothing of 36A., which comprises (a) forms Aqueous wash in washing container and be situated between Matter, the Aqueous wash medium is comprising (i) water, (ii) clothing, (iii) laundry detergent composition with (iv) according to aforementioned paragraphs Capsule described in middle either segment, wherein the water sensitivity composition includes inorganic bleaching agents composition；(c) in the Aqueous wash The clothing is washed in medium, wherein the water sensitivity combines until reaching at least about 10 minutes delay times washing cycle Object is just discharged into the Aqueous wash medium from the capsule.

Method of the 37A. as described in paragraph 36A, wherein by the capsule and the laundry detergent composition with such as paragraph The form of product described in either segment is added to the washing container in 33 to 35.

Method of the 38A. as described in paragraph 36A or 37A, wherein the clothing is at the end of washing without due to the capsule The visible residue of shell dissolution and generation.

Method of the 39A. as described in paragraph 36A either segment into 38A, wherein delay time washing cycle is at least about 15 minutes.

A kind of method for sustained release water sensitivity composition into water-based liquid medium of 40A., which comprises (a) capsule according to either segment in aforementioned paragraphs is provided, wherein the water sensitivity composition includes cleaning combination；(b) The capsule is added to the water-based liquid medium comprising water；And dissolve the capsule shells (c) to discharge the cleaning combination Object is into the water-based liquid medium, wherein reaching selected until the capsule is added to the water-based liquid medium Delay time, the cleaning combination are just discharged into the water-based liquid medium from the capsule.

Method of the 41A. as described in paragraph 40A, wherein the delay time is at least about 10 minutes.

Method of the 42A. as described in paragraph 40A, wherein the delay time is at least about 15 minutes.

Embodiment

Bleach-compatible method A (method A) test

By the water-soluble articles of sustained release to be tested, solubility and/or inorganic bleaching agents compatible characteristics (for example, root According to the capsule of present disclosure, water-soluble pouch or other) use 1:1 (wt%) sodium carbonate and SODIUM PERCARBONATE mixed-powder of 5.8g Or the compressed tablets load of the identical material of 10g, and seal.The bleaching agent piece of compacting may include stearic acid as adhesive, and use Compact technique preparation well known to those skilled in the art.Suitable bleaching agent dusty material derives from Solvay Chemicals.It should Product it is fixed using 0.5 inch of (12.7mm) metal cylinder mould of vinyl (vinyl) coating and be immersed under stiring containing In the 600ml beaker of 40 DEG C of deionized waters of 500ml.Water is adjusted to pH 7, submergence later includes the metal cylinder mould of product.? After submerging pouch, using pH probe monitoring water pH and record per minute until reaching 9.5 or higher pH, or until having been subjected to Go to 20 minutes (or 30 minutes or 40 minutes or 50 minutes or 60 minutes or 100 minutes or 120 minutes, such as wherein capsule It is intended for the longer sustained release time).Observe and record the integrality and dissolution properties of product.

The feature of suitable property of the sustained release capsule disclosed herein in 40 DEG C of water be by start in test (that is, Submergence product) about 8 minutes or increase suddenly from pH caused by product releasable material later.More generally, it is tested according to method A, Capsule shells keep complete at least 8 minutes, 10 minutes, 12 minutes or 14 minutes and/or up to 12 minutes, 14 minutes, 16 minutes, 18 Minute or 20 minutes.Aforementioned release time is particularly suitable for sustained release inorganic bleaching agents into laundry wash medium.For The other application that capsule includes and delivers the composition other than inorganic bleaching agents and/or be delivered in different aqueous mediums, It is tested according to method A, capsule shells can keep complete for example at least 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 Minute, 50 minutes or 60 minutes and/or up to 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, 80 minutes Or 100 minutes (for example, 5 minutes or 10 minutes to 15 minutes or 20 minutes, 10 minutes or 15 minutes to 20 minutes or 30 minutes, 20 minutes or 30 minutes to 40 minutes or 50 minutes or 40 minutes or 50 minutes to 60 minutes, 80 minutes or 100 minutes).For These other applications, the test of method A still can be used for determining or characterizing the release time of capsule (for example, wherein method A's is inorganic Bleaching agent serves as the pH marker of the release time for determining or characterizing capsule, even if capsule can be used in intended application Deliver the composition other than inorganic bleaching agents).In alternative, any other suitable marker can be used.Example Such as, in the alternative of inorganic bleaching agents, marker can be another pH marker (for example, the acidity compatible with capsule material Or alkaline matter, because it does not influence its solubility) or pigment, dyestuff or other colorants.Desired release time can be related to As the originally capsule of manufacture (that is, as formed) and/or they can reflect and for example stored up under 80%RH and 38 DEG C of environment of control Deposit the capsule of such as 2 weeks or 4 weeks test phases.Such property of the inorganic bleaching agents composition of method A can correspond to using About 15 to 20 minutes ingredient hangovers in the commercially available automatic washing machine period of nominal 40 DEG C of washing waters.

Bleach-compatible method B (method B) test

Test is by water in the Siemens S16-79 washing machine or equivalent using program Koch/Bunt (cotton/coloring) Sustained release, solubility and/or the bleach-compatible feature of the water-soluble articles of soluble polymer preparation.SIEMENS board There are S16-79 automatic washing machine 65 liters of cylinder capacity and variable temperature to select.Test sample is as above for bleach-compatible side It is prepared described in method A.The temperature of washing water is 20 DEG C, 40 DEG C or 60 DEG C.The water hardness is 250ppm CaCO₃(14 ° of d, Germany Hardness).Wash load is 3kg, by 2 sheets (1.5x1.5m ISO 2267), 4 pillowcases (0.8x0.8m ISO 2267) and 3 diablement fort towel (cotton is through bleaching) compositions.The dissolution time of method B corresponds to the time for reaching 9.5 or higher pH, such as logical Cross the measurement of pH probe.Suitable property was characterized in that by using nominal 40 DEG C of washing waters in commercially available automatic washing machine week In phase, in about 10 minutes, 12 minutes or 15 minutes to about 15 minutes, 20 minutes or 25 minutes caused by product releasable material PH increases suddenly.As above, included for capsule and delivering the composition other than inorganic bleaching agents and/or be delivered to difference Other application in aqueous medium, according to the test of method B, capsule shells can keep complete at least 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes and/or up to 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 points Clock, 60 minutes, 80 minutes or 100 minutes (for example, 5 minutes or 10 minutes to 15 minutes or 20 minutes, 10 minutes or 15 minutes extremely 20 minutes or 30 minutes, 20 minutes or 30 minutes to 40 minutes or 50 minutes, 40 minutes or 50 minutes to 60 minutes, 80 minutes or 100 minutes).Desired release time, which can be related to capsule as originally manufactured (that is, as formed) and/or they, to be reflected in The capsule of such as 2 weeks or 4 weeks test phases is stored under 80%RH and 38 DEG C of environment of control.

Residue of doing washing is tested

In the MIELE board W3033 front load formula rinsing maching or equivalent selected with 71 liters of cylinder capacity and variable temperature Middle test water solubility and the trend that laundry residue is left by product prepared by water-soluble polymer.The temperature of washing water is mark Claim 20 DEG C (or unheated), 40 DEG C or 60 DEG C.Standard wash load is about 2.9kg, by 4 towels (cotton), 2 bath towels (cotton or cotton/PET are blended for (cotton), 4 pillowcases (cotton or cotton/PET blend) and 1 big bed sheet (queen flat sheet) Object) composition.Lighter wash load is about 1.9kg, is made of 1 bath towel and 1 pillowcase.Heavier wash load is about 3.7kg, by 4 towels, 3 bath towels, 4 pillowcases and 1 big bed sheet composition.Test article is as above for bleach-compatible method A It is described to be prepared, and a product is placed in closed pillowcase and (knots and fasten) each wash load for test.So Conventional wash cycle carries out about 61 minutes afterwards, optionally followed by the rinse cycle for carrying out about 36 minutes.In washing cycle, rinsing week At the end of phase or both, clothing is taken out from washing machine and visually inspects residue (for example, undissolved capsule shells or pouch film are poly- Close object) presence, no matter on closed pillowcase or other places.The expectation water solubility feature of typical clothes wash temperature It is no visible any residue.

Suitable property in the clothes-washing environment of sustained release capsule disclosed herein is characterized in that, as described above about 20 DEG C at a temperature of in the range of about 25 DEG C in unheated washing cycle with clothing (for example, having small, standard or big ginseng Examine wash load) together wash 61 minutes when capsule do not left on clothing any visible residue (for example, based on visually inspection It looks into).Optionally or additionally, capsule is at a temperature of (i) is in the range of about 20 DEG C to about 25 DEG C in unheated washing cycle In with clothing (for example, with small, standard or big reference wash load) together washing 61 minutes, then (ii) at about 20 DEG C extremely When rinsing 36 minutes together with clothing at a temperature of in the range of about 25 DEG C, any visible residue is not left suitably.

Embodiment 1: sustained release capsule

It is formed according to present disclosure and capsule substantially as shown in Figure 1 is to evaluate its storage stability, delay is released Put property and solubility properties.Shell element with two forms capsule shells, and the cooperation shell element passes through injection molding PVOH homopolymer composition and formed.PVOH homopolymer composition includes the cold water soluble PVOH of about 80wt.% to 90wt.% Homopolymer (8cP solution viscosity, 88% degree of hydrolysis), the water soluble hydroxy plasticizer of about 9wt.% to 15wt.% and about The a small amount of additive (such as lubricant, release agent, filler, incremental agent, anticaking agent and antitack agent) of 0.5wt.% to 2wt.%. Shell element has the nominal wall thickness of about 35 mils (890 μm), but the end wall portion of shell element has (710 μm of about 28 mil；By T in Fig. 1₂Indicate) relatively thin wall.1:1 (by weight) mixture of SODIUM PERCARBONATE and sodium carbonate is (total It 5.8g) is added to capsule bottom, then it is capped with capsule top and carries out water-stop.The capsule of assembly has about 22mm OD Outer diameter and about 55mm height.Then it is about 700 μm and corresponding that the bottom of capsule, which provides diameter with No. 22.5 needle-penetrations, The pin hole that aspect ratio (L/D) is about 1.

Comparative example 2-3: inorganic bleaching agents pouch

Comparative example 2 and 3 includes that the water-solubility membrane of 4 mil thicks formed using conventional hot forming techniques by PVOH homopolymer is small Bag.Pouch uses the 10g- piece of SODIUM PERCARBONATE and sodium carbonate (1:1 by weight) to fill as inorganic bleaching agents, then seals.? In comparative example 2, inorganic bleaching agents piece has with a thickness of about 20 mils, the PEG- generally in the range of 15 mils to 25 mil 6000 coating.In comparative example 3, inorganic bleaching agents piece is not coated.

Embodiment 4, comparative example 5-6: pouch/capsule/bleaching agent product

Embodiment 4 includes the water-solubility membrane pouch of 3 mil thicks formed using conventional hot forming techniques by PVOH copolymer. It will be placed in pouch according to the sustained release capsule (including inorganic bleaching agents) of embodiment 1 before sealing.Then pouch is used For No. 22.5 needle-penetrations to provide pin hole (about 700 μm of diameter) in pouch wall, the pin hole provides internal pouch and (i) pouch External environment and (ii) communicated by the gaseous fluid of both inside capsule volumes of capsule shells pin hole.Resulting pouch/glue Capsule/inorganic bleaching agents product corresponds generally to the right side of pouch 400 as shown in Figure 2 (that is, including capsule 100 but not wrapping Second compartment 454 containing detergent 460).

Other than formation pin-free in pouch wall, comparative example 5 is same as Example 4.Therefore, internal pouch only with The internal capacity of capsule shells, rather than be in fluid communication with the ambient outside air of pouch.

Other than formation pin-free in capsule shells or pouch wall, comparative example 6 is same as Example 4.Therefore, pouch It is internal not to be in fluid communication with the ambient outside air of the internal capacity of (i) capsule shells or (ii) pouch.

Embodiment 7: gas generates test result

By pouch/capsule/inorganic bleaching agents product (each three of pouch/capsule combination embodiment 4 and comparative example 5-6 Repeat) it is stored 4 weeks in the environment of the control at 80% relative humidity and 38 DEG C.The elaboration of these embodiments passes through from external environment Water-soluble polymer wall and pin hole (in the presence of) effect of vapor in internal capsule volume is penetrated into, wherein vapor contacts Inorganic bleaching agents composition is to release hydrogen peroxide gas and correspondingly generation oxygen and other vapor.The gas induced by water The flatulence (that is, volume expansion or deformation) of pouch caused by body generates and/or capsule is undesirable, because it can lead to The physical damage of pouch and/or capsule during storage.This physical damage can reduce the useful shelf life of product, such as by permitting Perhaps the content (for example, laundry detergent compositions, inorganic bleaching agents or other compositions) of pouch and/or capsule is from the system originally sealed Product are leaked out or are escaped and/or by change/elimination capsule sustained release property (for example, by introducing capsule 's content It is discharged immediately or substantially earlier than expeced time when water-based liquid medium).In addition, even if the degree of flatulence does not lead to any function On defect (such as physical damage of capsule or pouch), may also lead to undesirable Consumers' Acceptance, such as produce The impression of product defect.

Following table 1 indicates that the gas induced from water generates the result of test.According to table 1, it is seen that at 38 DEG C/80%RH 4 weeks in, the combination of pin hole prevents whole flatulence in capsule shells and package both pouch, appoints so that capsule and pouch are not shown What visible expansion or cubic deformation (embodiment 4).The result illustrates that capsule and pouch keep structural integrity during storage Property and keep capsule sustained release property ability.In contrast, at least one in two pin holes is lacked in control sample It is a to lead to capsule or pouch flatulence (comparative example 5-6).This flatulence illustrates the product to the permeability of atmospheric water (even if lacking In the case where few pin hole), the neurological susceptibility and product breakdown/degradation danger that excess air (oxygen) is generated.Although comparative example The flatulence of 5 display pouches, but which illustrate the profitabilities about capsule (it includes the pin hole discharged for the gas of generation) Matter, because the capsule of comparative example 5 keeps its shape and structural intergrity during storage, although the pouch flatulence outside capsule.

1. gas of table generates test result

Embodiment 8: bleach-compatible method A result

The delay of test the inorganic bleaching agents capsule according to embodiment 1 and the inorganic bleaching agents pouch according to comparative example 2 is released Put property, as determined by bleach-compatible method A reach 9.5 pH value at 40 DEG C in water needed for the time scale Show and (sees above).(i) as originally formed, (ii) is in ambient storage conditions (room temperature and unsteered humidity；It is expressed as " Amb (n) " n=2 under), after 4 and 6 weeks time, and the storage condition of the control of (iii) under 38 DEG C and 80% relative humidity Middle n=2, the test capsule that (is expressed as " 38/80 (n) ") after 4 and 6 weeks time.The pouch that test was such as originally formed.

Following table 2 indicates the result of bleach-compatible method A test.As seen from Table 2, it was unexpectedly found that, it is real Apply pin hole in the capsule shells of example 1 presence do not destroy the sustained release property of capsule (for example, by the Premature disintegration of capsule and/ Or by allowing the content of capsule to discharge too early by pin hole).In addition, the data be shown in extend the time in it is relatively uniform Sustained release property, no matter storing in environmental condition or under controlled conditions.

2. bleach-compatible method A result of table

It by experiment, is visually observed capsule shells and tends to leak through the bottom of capsule and discharge its inorganic bleaching agents powder, the bottom of by Relatively thin wall thickness (about 7 mils (178 μm)) in portion causes.Therefore, it is contemplated that can be by with substantially homogeneous wall thickness Capsule shells design to obtain improved dissolution uniformity.In addition, wall thickness can be increased or decreased for given application to increase respectively Add deduct few capsule release or dissolution time (for example, as indicated by method A or method B compatibility test).

Embodiment 9: capsule dissolution/residue test result

The inorganic bleaching agents capsule according to embodiment 1 and the inorganic bleaching agents pouch according to comparative example 2-3 are tested in typical case The ability of the residue on clothing is dissolved and avoided in washing cycle, and (seeing above) is such as indicated by laundry residue test. (i) as originally formed, (ii) is in ambient storage conditions (room temperature and unsteered humidity；Be expressed as " Amb (n) ") under n=2,4 After 6 weeks time, and (iii) n=2,4 and 6 weeks in the storage condition of the control under 38 DEG C and 80% relative humidity Time after the test capsule that (is expressed as " 38/80 (n) ").The pouch that test was such as originally formed.Product is added in various ways It adds to small, standard or big wash load and is subjected to (nominal the 60 of unheated (nominal 20 DEG C), warm (nominal 40 DEG C) or heat DEG C) 61 minute washing cycle, subsequent 31 minutes rinse cycles.Actual temperature washing cycle is measured and recorded (in such as following table 3 Shown in bracket), (" after washing ") and the (" drift at the end of rinse cycle at the end of washing cycle and before rinse cycle After washing ") presence or absence of observation visible residue.

Following table 3 indicates the result of laundry residue test.As seen from Table 3, the delay according to present disclosure is found Release capsule (embodiment 1) does not leave laundry residue usually after rinse cycle, in most extreme accelerated ageing conditions (38 DEG C/80%RH, 6 weeks) under except.This feature is significant, because the wall of capsule shells is thicker than the inorganic bleaching coated with PEG significantly The film of the comparative example 2 of agent.

The laundry residue test result of table 3.

Laundry residue key point: 0- is completely absent any residue through visual inspection；

1- visually notices few, immaterial residue once in a while；

2- visually notices consistent few, immaterial residue；With

3- visually notices consistent abundant residues object

Foregoing description provides only for being clearly understood that, and should not be understood unnecessary limitation since then, because at this Modification in the range of invention can be obvious for those of ordinary skill in the art.

Through this specification and following following claims, unless the context requires otherwise, otherwise word " includes (comprise) " and modification for example " contains (comprises) " and " including (comprising) " is interpreted as implying to include institute It states integer or step and perhaps the group of integer or step but is not excluded for the group of any other integer or step or integer or step.

Through this specification, by composition be described as include component or material when, unless otherwise described, be otherwise expected group Closing object can also substantially be made of any combination of the component or material or by the component or any combination group of material At.Similarly, by method be described as include particular step when, unless otherwise described, otherwise be expected method can also substantially by Any combination of the step is formed or is made of any combination of the step.Illustratively the disclosed present invention is suitable herein Locality can implement there is no not specifically disclosed any element herein or step.

What the implementation of method disclosed herein and its single step can provide manually and/or by means of or by electronic equipment Automation carries out.Although having referred to specific embodiment describes method, those of ordinary skill in the art will easily recognize It arrives, the other way for executing effect relevant to these methods can be used.For example, unless otherwise stated, otherwise various steps Sequence can change without departing substantially from the range or spirit of this method.In addition, can be combined in some single steps, omit or It is further subdivided into other step.

All patents, announcement and the bibliography being mentioned herein pass through reference herein and are entirely incorporated into.If in the disclosure Hold and conflict between patent, announcement and the bibliography being incorporated to, then should be subject to present disclosure.

Claims

1. a kind of for delivering the sustained release capsule of cleaning combination, the capsule includes:

(a) comprising water-soluble polymer and the capsule shells of internal capsule volume are limited, wherein

(i) capsule shells have the substantially homogeneous wall thickness in the range of about 500 μm to about 5000 μm,

(ii) the capsule shell wall has the local thickness in about the 50% of the average wall thickness for substantially crossing over entire capsule shells,

(iii) capsule shells include pin hole, and the pin hole is sized with shape so that (A) is allowed in the internal capsule Gaseous fluid communicates between environment outside volume and the capsule shells, and (B) is limited in the internal capsule volume and institute Liquid fluid between external environment is stated to communicate,

(iv) capsule shells cooperate comprising two or more in the form slidably engaged described to limit jointly together The capsule shells element of capsule shells and the internal capsule volume,

(v) each capsule shells element includes the water-soluble polymer, and

(vi) at least one capsule shells element includes the pin hole；With

(b) cleaning combination for sustained release being contained in the internal capsule volume, wherein the cleaning combination It is not the water sensitivity composition that gas can be produced when contacting at least one of liquid water and steam.

2. a kind of for delivering the capsule of air exhaust combination object, the capsule includes:

(i) capsule shells have the wall thickness in the range of about 500 μm to about 5000 μm,

(ii) capsule shells include pin hole, and the pin hole is sized with shape so that (A) is allowed in the internal capsule Gaseous fluid communicates between environment outside volume and the capsule shells, and (B) is limited in the internal capsule volume and institute Liquid fluid between external environment is stated to communicate,

(iii) capsule shells cooperate comprising two or more in the form slidably engaged described to limit jointly together The capsule shells element of capsule shells and the internal capsule volume,

(v) each capsule shells element includes the water-soluble polymer, and

(vi) at least one capsule shells element includes the pin hole；And

(b) it is contained in the air exhaust combination object contacted in the internal capsule volume and with the capsule shell wall, wherein in described Portion's capsule volume is free of the water sensitivity composition that gas can be produced when contacting at least one of liquid water and steam.

3. capsule as claimed in claim 2, wherein the pin hole has the diameter in the range of about 10 μm to about 1500 μm (D)。

4. the capsule as described in any one of Claims 2 or 3, wherein the pin hole has length (L) and diameter (D): corresponding L/D ratio in the range of about 0.01 to about 100.

5. the capsule as described in any one of Claims 2 or 3, wherein the air exhaust combination object includes volatile compositions, institute State the volatile component that the volatile compositions can be discharged in volatile compositions in gaseous form.

6. the capsule as described in any one of Claims 2 or 3, wherein the air exhaust combination object includes that can issue essence gas Essence combination.

7. capsule as claimed in claim 6, wherein the essence combination includes the solid matrix for loading essence.

8. the capsule as described in any one of Claims 2 or 3, wherein it is not liquid water and steam that the composition, which is included in, Reactive component in the presence of can produce the gas-generating agent composition of gas.

9. the capsule as described in any one of Claims 2 or 3, wherein the capsule further comprises being contained in the internal sizes Additional composition in capsule volume, and at least one of the composition and the additional composition are intended for delay and release It puts.

10. the capsule as described in any one of claims 1 or 2, wherein the internal sizes capsule volume is in about 0.1ml to about In the range of 100ml.

11. the capsule as described in any one of claims 1 or 2, wherein range of the wall thickness at about 500 μm to about 1500 μm It is interior.

12. the capsule as described in any one of Claims 2 or 3, wherein the capsule shells have substantially homogeneous wall thickness.

13. capsule as claimed in claim 12, wherein the capsule shells wall has substantially being averaged across entire capsule shells Local thickness in about the 50% of wall thickness.

14. the capsule as described in any one of claims 1 or 2, wherein the water-soluble polymer is hot formed.

15. the capsule as described in any one of claims 1 or 2, wherein the water-soluble polymer has about 4cP at 20 DEG C 4% solution viscosity in the range of to about 23cP.

16. the capsule as described in any one of claims 1 or 2, wherein the water-soluble polymer is selected from by polyvinyl alcohol, gathers Aziridine, polyalkylene oxide, polyacrylamide, cellulose ether, cellulose esters, cellulose amides, gathers at polyvinylpyrrolidone Vinyl acetate, polyamide, gelatin, methylcellulose, carboxymethyl cellulose and its salt, dextrin, ethyl cellulose, ethoxy are fine Tie up the group of element, hydroxypropyl methyl cellulose, maltodextrin, their copolymer, their blend and their combination composition In.

17. the capsule as described in any one of claims 1 or 2, wherein the water-soluble polymer includes polyvinyl alcohol.

18. capsule as claimed in claim 17, wherein the polyvinyl alcohol has the water in the range of about 75% to about 99% Xie Du.

19. capsule as claimed in claim 17, wherein the polyvinyl alcohol includes substantially by vinyl alcohol monomer repetitive unit With the polyvinyl alcohol copolymer of vinyl acetate monomer repetitive unit composition.

20. capsule as claimed in claim 17, wherein the polyvinyl alcohol includes to contain vinyl alcohol monomer repetitive unit, acetic acid The polyvinyl alcohol copolymer of vinyl acetate monomer repetitive unit and the monomeric repeating unit of at least one other type.

21. the capsule as described in any one of claims 1 or 2, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 5 minutes to 20 minutes complete.

22. the capsule as described in any one of claims 1 or 2, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 20 minutes to 50 minutes complete.

23. the capsule as described in any one of claims 1 or 2, wherein as measured by bleach-compatible method A, when It is formed by when capsule shells are immersed in the water for the temperature for being heated to about 40 DEG C and keeps about 50 minutes to 100 minutes complete.

24. the capsule as described in any one of claims 1 or 2, wherein the composition be selected from by laundry detergent composition, In the group that fabric intensifier, organic bleaches, essence and their combination form.

25. capsule as claimed in claim 24, wherein the capsule is at a temperature of in the range of about 20 DEG C to about 25 DEG C Visible residue is not left on clothing when washing together with clothing in unheated washing cycle 61 minutes.

26. capsule as claimed in claim 24, wherein the capsule is when the temperature of (i) in the range of about 20 DEG C to about 25 DEG C Under wash 61 minutes together with clothing in unheated washing cycle, then (ii) is in the range of about 20 DEG C to about 25 DEG C At a temperature of when rinsing 36 minutes together with clothing, visible residue is not left on clothing.

27. a kind of capsule for delivering volatile composition, the capsule includes:

It (a) include polyvinyl alcohol and the water-soluble glue softgel shell for limiting internal capsule volume, in which:

(i) capsule shells have the wall thickness in the range of about 500 μm to about 3000 μm, and

(ii) capsule shells include pin hole, and the pin hole is sized with shape so that (A) is allowed in the internal capsule Gaseous fluid communicates between volume and the external environment of the capsule shells, and (B) is limited in the internal capsule volume and institute Liquid fluid between external environment is stated to communicate,

(v) each capsule shells element includes polyvinyl alcohol, and

(vi) at least one capsule shells element includes the pin hole；With

(b) volatile compositions being contained in the internal capsule volume, the volatile compositions can be with gas procedure The volatile component of the volatile compositions is discharged.

28. capsule as claimed in claim 27, wherein the capsule shells have the base in the range of about 500 μm to about 1500 μm This uniform wall thickness.

29. capsule as claimed in claim 27, wherein the capsule further includes:

(c) additional composition being contained in the internal capsule volume, wherein the additional composition is intended for from described Capsule sustained release.

30. capsule as claimed in claim 29, wherein the additional composition is selected from micro- by the perfume particles and essence that coat In the group of capsule composition.

31. the capsule as described in any one of claim 27 to 30, wherein the internal sizes capsule volume be free of when and liquid water With the water sensitivity composition that can produce gas when the contact of at least one of vapor.

32. a kind of product comprising laundry detergent composition, the product includes:

It (a) include water-solubility membrane and the water-soluble pouch for limiting (i) inner pouch volume He (ii) pin hole, the pin hole is set Size and shape is in fluid communication with being allowed between the environment outside the inner pouch volume and the water-soluble pouch；

(b) capsule according to any one of claim 1 or 2 being contained in the inner pouch volume, wherein described Capsule shells pin hole and the water-soluble pouch pin hole are in fluid communication；With

(c) laundry detergent composition being contained in the inner pouch volume.

33. product as claimed in claim 32, in which:

(i) the inner pouch volume include at least the second of (A) first compartment and (B) and the first compartment physical separation every Room；

(ii) first compartment limits the pouch pin hole, and includes the capsule；And

(iii) second compartment includes the laundry detergent composition.

34. product as claimed in claim 32, wherein the water-solubility membrane includes water-soluble polymer, the water-soluble polymeric Object can be identical or different with the water-soluble polymer of the capsule shells.

35. a kind of method for washing clothing, which comprises

(a) Aqueous wash medium is formed in washing container, the Aqueous wash medium includes (i) water, (ii) clothing, (iii) Laundry detergent composition and (iv) basis (A) capsule described in claim 1, or (B) capsule as claimed in claim 2, Wherein the air exhaust combination object includes cleaning combination；And

(b) clothing is washed in the Aqueous wash medium；

Wherein until reaching selected delay time washing cycle, institute after adding the capsule to the water-based liquid medium Cleaning combination is stated just to discharge from the capsule.

36. method as claimed in claim 35 adds the capsule and the laundry detergent composition in the form of product It is added to the washing container, the product includes:

(b) capsule being contained in the inner pouch volume, wherein the capsule shells pin hole and the water solubility are small Bag pin hole is in fluid communication；With

(c) laundry detergent composition being contained in the inner pouch volume.

37. method as claimed in claim 35, wherein the clothing is at the end of washing without due to capsule shells dissolution And the visible residue generated.

38. method as claimed in claim 35, further comprises:

(c) Aqueous wash medium is removed from the washing container, does not remove the clothing and the capsule；

(d) aqueous rinse medium is formed in the washing container, the aqueous rinse medium was cleaned comprising (i) water, (ii) Clothing and (iii) described capsule；And

(e) clothing is rinsed in the aqueous rinse medium；

Wherein the selected delay time washing cycle long enough is so that the cleaning combination is discharged into institute from the capsule It states in aqueous rinse medium.

39. method as claimed in claim 35, further comprises:

(c) Aqueous wash medium is removed from the washing container, does not remove the clothing；

(d) aqueous rinse medium is formed in the washing container, the aqueous rinse medium includes that (i) water and (ii) were cleaned Clothing；And

(e) clothing is rinsed in the aqueous rinse medium；

Wherein selected delay time washing cycle is short enough so that the cleaning combination is discharged into institute from the capsule It states in Aqueous wash medium.

40. a kind of method for delayed release compositions into water-based liquid medium, which comprises

(a) it provides according to (i) capsule described in claim 1, or (ii) capsule as claimed in claim 2, wherein the row Gas composition includes cleaning combination；

(b) capsule is added to the water-based liquid medium comprising water；And

(c) capsule shells are dissolved to discharge the cleaning combination into the water-based liquid medium, wherein by the capsule It is added to after the water-based liquid medium until reaching selected delay time, the cleaning combination is just released from the capsule It is put into the water-based liquid medium.

41. method as claimed in claim 40, wherein the delay time is at least about 10 minutes.

42. method as claimed in claim 40, wherein the delay time is at least about 15 minutes.